For example by hbaKk15

VIEWS: 35 PAGES: 68

									Vol. 56 No. 137 Wednesday, July 17, 1991 p 32688

>>>> This article, FR94, is divided into five files. This is File A: Corrections for Part 261
through Part 270. Technical Amendments to Part 261 through 3.2.7.4 of Appendix IX to Part
266. <<<<



ENVIRONMENTAL PROTECTION AGENCY

40 CFR Parts 260, 261, 264, 265, 266, 270, and 271

[EPA/OSW-FR-91- SWH-FRL-39689]

Burning of Hazardous Waste in Boilers and Industrial Furnaces

AGENCY: Environmental Protection Agency (EPA).

ACTION: Final rule: corrections; technical amendments.



SUMMARY: On February 21, 1991, the Environmental Protection Agency (EPA) published a
final rule to regulate air emissions from the burning of hazardous waste in boilers and industrial
furnaces (56 FR 7134). Today's notice corrects typographical and editorial errors that appeared in
the regulatory text, including corrections to appendices II and III, and adds two appendices,
appendix IX and appendix X, to part 266. Appendices IX and X were not ready at the time of
publication; therefore, a note was placed in the appropriate location in the rule to inform readers
that these appendices were to be published at a later date. Copies of these appendices were,
however, made available to the public through the RCRA Docket maintained at EPA and
through the National Technical Information Service (NTIS).

EFFECTIVE DATE: The effective date of the rule remains August 21, 1991.

FOR FURTHER INFORMATION CONTACT: For general information, contact the RCRA
Hotline at (800) 424-9346 (toll-free) or (703) 920-9810. For more specific aspects of the final
rule, contact Shiva Garg, Office of Solid Waste (0S-322), U.S. Environmental Protection
Agency, 401 M Street, SW., Washington, DC 20460 (703) 308-8460.

>>>> Preamble has not been included in this file. <<<<

A. Technical Corrections

       In rule document number 91-2667, beginning on page 7134 in the Federal Register
published on Thursday, February 21, 1991, make the following corrections:
PART 261-[AMENDED]

       1. On page 7206, third column, in amendment 2 to part 261, add the following at the
beginning of line 3 of the amendatory language of § 261.2: ", paragraph (d)(3) as (d)(4) and
paragraph (d)(4) as (d)(5)". The corrected amendatory language will read as follows:

        "2. Section 261.2 is amended by redesignating paragraph (d)(2) as (d)(3), paragraph
(d)(3) as (d)(4), and paragraph (d)(4) as (d)(5), and adding a new paragraph (d)(2) to read as
follows:"

PART 266-[AMENDED]

§ 266.100 [Corrected]

       2. On page 7208, second column, in § 266.100(b)(2), line 3, replace the period after
"recovery" with a semicolon.

       3. On page 7208, second column, in § 266.100(b)(3), line 7, change "§ 261.5 of this
chapter." to "§ 261.5 of this chapter; and ".

§ 266.102 [Corrected]

        4. On page 7209, second column, in § 266.102(b)(1), line 12, change "for the Evaluation
of Solid Waste" to "for Evaluating Solid Waste".

       5. On page 7210, first column, in § 266.102, the paragraph designated as "(d)(4)(iii)(D)"
should be designated as "(d)(4)(iv)".

       6. On page 7210, third column, in § 266.102(e)(4)(i)(C), line 1, insert "A" between "(C)"
and "sampling".

      7. On page 7211, second column, in § 266.102(e)(6) heading, line 1, change
"paramenters" to "parameters".

      8. On page 7211, third column, in § 266.102(e)(6)(i)(B)(1)(ii), line 2, change "means" to
"mean".

       9. On page 7211, third column, at two locations: In lines 30 and 59, the number "2" in
each subparagraph (2) heading of § 266.102(e)(6)(i)(B) and § 266.102(e)(6)(ii)(B), respectively,
should be italicized.

       10. On page 7211, third column, in § 266.102(e)(6)(ii), line 10, change "opeator" to
"operator".
       11. On page 7211, third column, in § 266.102(e)(6)(ii)(B)(2), lines 3 and 4, change
"arithmetic mean of the most recent one hour block average for the average period" to
"arithmetic mean of one hour block averages for the averaging period".

      12. On page 7212, first column, in § 266.102(e)(6)(iv)(B), line 15, delete the comma
between "§ 266.106(f)" and "need".

§ 266.103 [Corrected]

       13. On page 7213, first column, in § 266.103(a)(1)(ii), line 7, insert "or" between "burn"
and "to".

        14. On page 7214, first column, in § 266.103(b)(2)(ii)(A), line 4, insert "and" between
"silver" and "thallium".

         15 On page 7214, first column, in § 266.103(b)(2)(ii)(B), line 3, the reference to
"(b)(ii)(A)" should read "(b)(2)(ii)(A)".

         16. On page 7214, first column, in § 266.103(b)(2)(ii)(D), line 4, the reference to
"(b)(ii)(B) or (b)(ii)(C)" should read "(b)(2)(ii)(B) or (b)(2)(ii)(C)".

        17. On page 7214, second column, line 3, in § 266.103(b)(2)(iv), change "paticulate" to
"particulate".

       18. On page 7214, second column, in § 266.103(b)(2)(v)(A)(5), line 2, change
"eqivalent" to "equivalent".

        19. On page 7214, second column, in § 266.103(b)(2)(v)(A)(5), line 4, replace the period
after "facility" with a semicolon.

          20. On page 7214, second column, in § 266.103(b)(2)(vi), line 3, change "HC1" to "HCl".

       21. On page 7214, third column, in § 266.103(b)(3)(ii), line 2, replace the semicolon after
"streams" with a colon.

          22. On page 7215, first column, in § 266.103(b)(5)(ii)(B), line 1, change "meat" to
"meet".

       23. On page 7215, first column, at two locations: in lines 38 and 66, the number "1" in
each subparagraph (1) heading of § 266.103(b)(5)(i)(B) and § 266.103(b)(5)(ii)(B), respectively,
should be italicized.

       24. On page 7215, first column, line 46, the number "2" in the subparagraph (2) heading
of § 266.103(b)(5)(i)(B) should be italicized.
       25. On page 7215, second column, line 4, the number "2" in the subparagraph (2) heading
of § 266.103(b)(5)(ii)(B) should be italicized.

       26. On page 7215, second column, in § 266.103(b)(5)(ii)(B)(2), line 3 and 4, change
"arithmetic mean of the most recent one hour block averages" to "arithmetic mean of one hour
block averages".

       27. On page 7215, second column, in § 266.103(b)(6) introductory text, lines 2 and 3,
change "[the effective date of this rule]" to "August 21, 1991".

      28. On page 7216, first column, in § 266.103(c), lines 1 and 2, delete "On or before
August 21, 1992", capitalize the "t" in "the", and insert "on or before August 21, 1992" in line 12
between "Director" and "a".

       29. On page 7216, first column, in § 266.103(c)(1), line 10, add "and all applicable
emissions standards" after "limits".

        30. On page 7216, second column, in § 266.103(c)(1)(iv), line 3, change "light-weighted"
to "light-weight".

        31. On page 7216, second column, in § 266.103(c)(1)(ix), line 8, replace the semicolon
after "(e))" with a colon.

       32. On page 7216, third column, in § 266.103(c)(1)(xi), lines 1, change "system" to
"systems", and in line 7, replace the semicolon after "(e))" with a colon.

        33. On page 7216, third column, in § 266.103(c)(1)(xii), line 8, replace the semicolon
after "(e))" with a colon.

        34. On page 7217, third column, in § 266.103(c)(4)(i)(C), line 2, change "test" to
"testing".

       35. On page 7217, third column, in § 266.103(c)(4)(ii)(B)(5), line 3, change "averge" to
"average".

        36. On page 7218, second column, in § 266.103(c)(4)(iv)(C)(2)(ii), lines 3 and 4, change
"the arithmetic mean of the most recent one hour block averages for the averaging period" to
"arithmetic mean of one hour block averages for the averaging period".

        37. On page 7218, third column, in § 266.103(c)(7)(i)(A), line 3, change "(1)" (one) to
"(1)" (lower case "el").

        38. On page 7218, third column, in § 266.103(c)(7)(i)(B), delete the last word "to" in line
1 and replace by "only for purposes of compliance testing (and pretesting to prepare for
compliance testing)".
        39. On page 7219, first column, in § 266.103(c)(7)(ii)(B)(1)(ii), line 7, insert a period
after "HCl/Cl2".

       40. On page 7219, first column, line 18, the number "2" in the subparagraph (2) heading
of § 266.103(c)(7)(ii)(B) should be italicized.

       41. On page 7219, third column, in § 266.103(g)(1), line 1, change "or" to "of".

§ 266.104 [Corrected]

       42. On page 7220, second column, in § 266.104(a)(1), change the equation:

                    1-Wout
DRE = [                        ]     X 100

                    Win

to:

                       Wout
DRE = [        1-      ]       X 100

                               Win

         43. On page 7220, third column, in § 266.104(a)(3), in line 12, change "tetrra-," to
"tetra-," and in line 16, the reference to "paragraph (a)" should read "paragraph (a)(1)".

        44. On page 7220, third column, in § 266.104(b)(2), lines 5 through 7, change "in
Hazardous Waste Incinerators, Boilers, and Industrial Furnaces" to "for Incinerators, Boilers, and
Industrial Furnaces Burning Hazardous Waste".

       45. On page 7221, first column, in § 266.104(c)(3), lines 3 through 6, change
"Performance Specifications for Continuous Emission Monitoring of Hydrocarbons for
Incinerators, Boilers and Industrial Furnaces" to "Performance Specifications for Continuous
Emission Monitoring of Hydrocarbons for Incinerators, Boilers, and Industrial Furnaces Burning
Hazardous Waste"; and in line 7, insert "and" between "CO" and "oxygen".

       46. On page 7221, second column, line 3, in § 266.104(e)(1), insert "(PCDDs)" after
"Dibenzo-p-Dioxins", and in line 6, replace the period at the end of the sentence after "part" with
a semicolon.

        47. On page 7221, second column, in § 266.104(e)(2), line 13, replace the period at the
end of the sentence after "TCDD" with a semicolon.

       48. On page 7221, second column, in § 266.104(e)(4), line 6, insert a before "2.2".
      49. On page 7221, third column, in § 266.104(f)(3)(iii), line 4, change "conducts" to
"conduct".

       50. On page 7222, first column, the paragraph designated as "(g)2." of § 266.104, should
be designated as "(g)(2)".

§ 266.106 [Corrected]

      51. On page 7222, second column, in § 266.106(a), line 9, change "for Evaluation Solid
Waste" to "for Evaluating Solid Waste".

       52. On page 7222, third column, in the equation after line 3, in § 266.106(b)(2)(i), change
"<1.0" to " 1.0", and change "n = numer of carcinogenic metals" to "n = number of
carcinogenic metals".

      53. On page 7222, third column, in § 266.106(b)(2)(ii)(B), line 2, insert "as defined in §
266.102(e)(6)(ii)" between "hours" and "with".

        54. On page 7222, third column, in § 266.106(b)(5), line 7, insert "shall be used" at the
end of the sentence before the period.

        55. On page 7223, first column, in § 266.106(b)(6), in the equation after line 15, change
lines 5 and 6 of the equation that read "K = physical stack height (meters); K = stack gas flow
rate (m3/second); and" to read: "H = physical stack height (meters); V = stack gas flow rate
(m3/second); and".

       56. On page 7223, second column, in § 266.106(c)(2), in the equation after line 12, delete
the minus sign after "AER(i)".

         57. On page 7223, third column, the equation in § 266.106(d)(3) is revised to read as
below:

n        Predicted Ambient
         Concentration(i)

                                       1.0


i=1
         Risk-Specific Dose(i)

        58. On page 7224, first column, in § 266.106(e), in line 8, change "each" to "a", and in
line 10, change "levels" to "level".

       59. On page 7224, first column, in § 266.106(f)(2)(ii) introductory text, delete the
semicolon after "metal".
        60. On page 7224, second column, line 3, in § 266.106(f)(2)(ii)(B), change "ratio" to
"ratios".

§ 266.107 [Corrected]

       61. On page 7224, second column, in § 266.107(a), line 4, change "provided by
paragraphs (b), (c), or (d) of" to "provided by paragraph (b) or (c) of".

       62. On page 7224, third column, in § 266.107(b)(2) heading, line 1, change "screen" to
"screening".

       63. On page 7224, third column, in § 266.107(b)(3), line 9, change "screen" to
"screening".

        64. On page 7225, first column, in § 266.107(d), change the paragraphs designated as
"(i)" and "(ii)" to "(1)" and "(2)".

       65. On page 7225, first column, in § 266.107(e), in line 3, insert "limit" between
"screening" and "provided", and in line 4, the reference to "Appendix I" should read "Appendix
II".

       66. On page 7225, first column, in § 266.107(h), line 5, change "his" to "this".

§ 266.108 [Corrected]

      67. On page 7225, first column, in § 266.108(a), in the heading, line 1, change
"Exemption" to "Exempt", and in the introductory text, line 5, change "section" to "subpart".

       68. On page 7225, second column, first column of the table entitled "Exempt Quantities
for Small Quantity Burner Exemption" in § 266.108(a)(1), insert "to" between "10.0" and "11.9".

       69. On page 7225, second column, in § 266.108(c), in the equation after line 7, change
"<1.0" to "1.0", and in the line after the equation that reads "Allowable Quantity Burned,
means the", delete the comma after "Burned".

§ 266.109 [Corrected]

        70. On page 7225, third column, in § 266.109(a)(1)(i), in line 4, change "of" to "on", and
in line 8, delete the apostrophe after "fuel" and replace it with an end quotation mark.

        71. On page 7226, first column, in § 266.109(a)(2)(iv) introductory text, line 3, change
the reference to "(a)(iii)" to "(a)(2)(iii)".

      72. On page 7226, first column, in § 266.109(a)(2)(iv)(A), line 2, change "componds" to
"compounds".
      73. On page 7226, first column, in § 266.109(b)(2), line 2, add "or adjusted Tier I"
between "I" and "metals".

§ 266.110 [Corrected]

          74. On page 7226, third column, line 4, in § 266.110(f)(3), insert "the" between "of" and
"fuel".

      75. On page 7227, third column, line 11, "§ 266.122" should correctly be designated as "§
266.112".

Part 266, Appendix I         [Amended]

       76. On page 7228, in appendix I to part 266, in the title for Table I-A, change
"Carcinogenic" to "Noncarcinogenic".

        77. On page 7230, in appendix I to part 266, Table I-D: under "Values for use in rural
areas", the first column "Beryllium" is moved so that it appears as the fifth column under
"Values for use in urban areas". Also under "Values for use in urban areas", in second column
under "Arsenic g/hr", change "9.6E + 01" corresponding to a terrain adjusted eff. stack ht. of 16
meters to "9.6E-01".

       78. On page 7230, in appendix I to part 266, Table I-E, in column 2, change "4.3-01"
corresponding to "Terrain adjusted eff. stack ht. (m)" of 12 meters in the first column to
"4.3E-01".

          79. On page 7231, appendix II to part 266 is corrected to read as follows:

Appendix II.-Tier I Feed Rate Screening Limits for Total Chlorine



                              Noncomplex Terrain                             Complex
                                                                             Terrain


Terrain-adjusted effective     Urban (g/hr)                  Rural (g/hr)     (g/hr)
stack height (m)



4                              8.2E + 01                     4.2E + 01        1.9E + 01
6                              9.1E + 01                     4.8E + 01        2.8E + 01
8                              1.0E + 02                     5.3E + 01        4.1E + 01
10                             1.2E + 02                     6.2E + 01        5.8E + 01
12                             1.3E + 02                     7.7E + 01        7.2E + 01
14                             1.5E + 02                     9.1E + 01        9.1E + 01
16                             1.7E + 02                     1.2E + 02        1.1E + 02
18                             1.9E + 02                     1.4E + 02        1.2E + 02
20                             2.1E + 02                     1.8E + 02        1.3E + 02
22                             2.4E + 02                     2.3E + 02        1.4E + 02
24                             2.7E + 02                     2.9E + 02        1.6E + 02
26                             3.1E + 02                     3.7E + 02        1.7E + 02
28                            3.5E + 02                    4.7E + 02                     1.9E + 02
30                            3.9E + 02                    5.8E + 02                     2.1E + 02
35                            5.3E + 02                    9.6E + 02                     2.6E + 02
40                            6.2E + 02                    1.4E + 03                     3.3E + 02
45                            8.2E + 02                    2.0E + 03                     4.0E + 02
50                            1.1E + 03                    2.6E + 03                     4.8E + 02
55                            1.3E + 03                    3.5E + 03                     6.2E + 02
60                            1.6E + 03                    4.6E + 03                     7.7E + 02
65                            2.0E + 03                    6.2E + 03                     9.1E + 02
70                            2.3E + 03                    7.2E + 03                     1.1E + 03
75                            2.5E + 03                    8.6E + 03                     1.2E + 03
80                            2.9E + 03                    1.0E + 04                     1.3E + 03
85                            3.3E + 03                    1.2E + 04                     1.4E + 03
90                            3.7E + 03                    1.4E + 04                     1.6E + 03
95                            4.2E + 03                    1.7E + 04                     1.8E + 03
100                           4.8E + 03                    2.1E + 04                     2.0E + 03
105                           5.3E + 03                    2.4E + 04                     2.3E + 03
110                           6.2E + 03                    2.9E + 04                     2.5E + 03
115                           7.2E + 03                    3.5E + 04                     2.8E + 03
120                           8.2E + 03                    4.1E + 04                     3.2E + 03



        80. On pages 7231 and 7232, appendix III to part 266 is corrected to read as follows:

Appendix III.-Tier II Emission Rate Screening Limits for Free Chlorine and Hydrogen Chloride



                Noncomplex terrain                                                  Complex terrain


Terrain-        Values for urban areas            Values for rural areas            Values for use in urban and
adjusted                                                                            rural areas
effective
stack height
 (m)             C12 (g/hr)       HC1 (g/hr)       C12 (g/hr)       HC1 (g/hr)       C12 (g/hr)       HC1 (g/hr)



4                8.2E + 01        1.4E + 03        4.2E + 01        7.3E + 02        1.9E + 01        3.3E + 02
6                9.1E + 01        1.6E + 03        4.8E + 01        8.3E + 02        2.8E + 01        4.9E + 02
8                1.0E + 02        1.8E + 03        5.3E + 01        9.2E + 02        4.1E + 01        7.1E + 02
10               1.2E + 02        2.0E + 03        6.2E + 01        1.1E + 03        5.8E + 01        1.0E + 03
12               1.3E + 02        2.3E + 03        7.7E + 01        1.3E + 03        7.2E + 01        1.3E + 03
14               1.5E + 02        2.6E + 03        9.1E + 01        1.6E + 03        9.1E + 01        1.6E + 03
16               1.7E + 02        2.9E + 03        1.2E + 02        2.0E + 03        1.1E + 02        1.8E + 03
18               1.9E + 02        3.3E + 03        1.4E + 02        2.5E + 03        1.2E + 02        2.0E + 03
20               2.1E + 02        3.7E + 03        1.8E + 02        3.1E + 03        1.3E + 02        2.3E + 03
22               2.4E + 02        4.2E + 03        2.3E + 02        3.9E + 03        1.4E + 02        2.4E + 03
24               2.7E + 02        4.8E + 03        2.9E + 02        5.0E + 03        1.6E + 02        2.8E + 03
26               3.1E + 02        5.4E + 03        3.7E + 02        6.5E + 03        1.7E + 02        3.0E + 03
28               3.5E + 02        6.0E + 03        4.7E + 02        8.1E + 03        1.9E + 02        3.4E + 03
30               3.9E + 02        6.9E + 03        5.8E + 02        1.0E + 04        2.1E + 02        3.7E + 03
35               5.3E + 02        9.2E + 03        9.6E + 02        1.7E + 04        2.6E + 02        4.6E + 03
40               6.2E + 02        1.1E + 04        1.4E + 03        2.5E + 04        3.3E + 02        5.7E + 03
45               8.2E + 02        1.4E + 04        2.0E + 03        3.5E + 04        4.0E + 02        7.0E + 03
50               1.1E + 03        1.8E + 04        2.6E + 03        4.6E + 04        4.8E + 02        8.4E + 03
55               1.3E + 03        2.3E + 04        3.5E + 03        6.1E + 04        6.2E + 02        1.1E + 04
60               1.6E + 03        2.9E + 04        4.6E + 03        8.1E + 04        7.7E + 02        1.3E + 04
65               2.0E + 03        3.4E + 04        6.2E + 03        1.1E + 05        9.1E + 02        1.6E + 04
70               2.3E + 03        3.9E + 04        7.2E + 03        1.3E + 05        1.1E + 03        1.8E + 04
75              2.5E + 03        4.5E + 04       8.6E + 03        1.5E + 05       1.2E + 03     2.0E + 04
80              2.9E + 03        5.0E + 04       1.0E + 04        1.8E + 05       1.3E + 03     2.3E + 04
85              3.3E + 03        5.8E + 04       1.2E + 04        2.2E + 05       1.4E + 03     2.5E + 04
90              3.7E + 03        6.6E + 04       1.4E + 04        2.5E + 05       1.6E + 03     2.9E + 04
95              4.2E + 03        7.4E + 04       1.7E + 04        3.0E + 05       1.8E + 03     3.2E + 04
100             4.8E + 03        8.4E + 04       2.1E + 04        3.6E + 05       2.0E + 03     3.5E + 04
105             5.3E + 03        9.2E + 04       2.4E + 04        4.3E + 05       2.3E + 03     3.9E + 04
110             6.2E + 03        1.1E + 05       2.9E + 04        5.1E + 05       2.5E + 03     4.5E + 04
115             7.2E + 03        1.3E + 05       3.5E + 04        6.1E + 05       2.8E + 03     5.0E + 04
120             8.2E + 03        1.4E + 05       4.1E + 04        7.2E + 05       3.2E + 03     5.6E + 04



Part 266, Appendix IV [Amended]

       81. On page 7232, in appendix IV to part 266, first column of the table, change "Methyl Ethyl
Katone" to "Methyl Ethyl Ketone", and in line 34, change "Metyl Parathion" to "Methyl Parathion".

Part 266, Appendix VII [Amended]
        82. On page 7234, first column, in appendix VII to part 266, in the table entitled "Metals-TCLP
Extract Concentration Limits": in the heading in the third column of the table, replace "Concentration limits
(mg/kg)" with "Concentration limits (mg/L)"; and add the following at the end of the table:

Thallium 7440-28-0 7 X E + 00

       83. On page 7234, third column, in appendix VII to part 266, in the table entitled
"Nonmetals-Residue Concentration Limits-Continued", delete 8 lines beginning with "Thallium" and
ending with "Thallium(l) sulfate.

Part 266, Appendix VIII [Amended]

        84. On page 7235, in appendix VIII to part 266, first column of the table entitled "PICS Found in
Stack Effluents", change "roform" to "chloroform" and "robenzene" to "chlorobenzene".

PART 270-[AMENDED]

§ 270.22 [Corrected]

        85. On page 7235, second column, in § 270.22(a)(2)(ii)(B), line 12, change "Test Methods for the
Evaluation of" to "Test Methods for Evaluating".

        86. On page 7235, second column, in § 270.22(a)(2)(ii)(C), line 5, the reference to "(a)(1)(ii)(B)"
should read "(a)(2)(ii)(B)".

        87. On page 7236, first column, in § 270.22(a)(5)(vii), line 4, change "feestocks" to "feedstocks".

        88. On page 7236, first column, in § 270.22(a)(6), line 1, change "trail" to "trial".

        89. On page 7236, second column, in § 270.22(a)(6), line 8, change "from from" to "from" i.e.
delete one "from" as it is duplicative.

        90. On page 7236, second column, in § 270.22(b)(1), line 2, change "minimze" to "minimize".

§ 270.42 [Corrected]

       91. On page 7237, first column, in § 270.42(g)(1) introductory text, line 3, change "wates" to
"wastes".
        92. On page 7237, first column, in § 270.42(g)(1)(i), line 5, change "effetive" to "effective".

         93. On page 7237, second column, in § 270.42(g)(1)(iv), in lines 1 and 2, delete "In the case of
Classes 2 and 3 modifications,"; in line 2, capitalize the "t" in "the"; and insert "Class 2 or 3" between
"complete" and "modification" so that paragraph (iv) reads as follows: "The permittee also submits a
complete Class 2 or 3 modification request within 180 days of the effective date of the rule listing or
identifying the waste, or subjecting the unit to RCRA Subtitle C management standards;".

        94. On page 7237, in appendix I to § 270.42, in line 1 of "L.5.", replace the period after
"requirements" with a colon.

        95. On page 7237, third column, in amendment 4 to part 270, the amendatory language is
corrected to read as follows: "4. In § 270.42, appendix I is amended by revising the heading of L and
items 1 through 4, 5a, 6, 7b, and 8 to read as follows:"

§ 270.66 [Corrected]

        96. On page 7237, third column, line 2, in § 270.66(b)(1), change "operation" to "operational".

        97. On page 7238, second column, in § 270.66(b)(4), line 8, change "107" to "266.107".

        98. On page 7238, at two locations, lines 13, 14, and 15, in § 270.66(c)(2)(i) and in lines 5 and 6
in § 270.66(c)(2)(ii), change "Test Methods for the Evaluation of Solid Waste" to "Test Methods for
Evaluating Solid Waste".

        99. On page 7238, third column, in § 270.66(c)(3)(vi), line 3, delete "and".

         100. On page 7238, third column, in § 270.66(c)(3)(vii), line 1, insert "air" between "any" and
"pollution".

        101. On page 7239, second column, in § 270.66(f)(3), line 10, replace the period after "standard"
with a semicolon.

        102. On page 7239, second column, in § 270.66(f)(8), line 5, change "is" to "in".

§ 270.33 [Corrected]

       103. On page 7239, third column, in § 270.73 at two locations, in paragraph (f), line 2, and in
paragraph (g), line 3, change "as" to "has".

       104. On page 7240, in § 271.1(j), Table 1, third column, replace "[insert FR page numbers]" with
"56 FR 7134-7240".

B. Technical Amendments

        For the reasons set out in the preamble, 40 CFR part 261 is amended as follows:

PART 261-IDENTIFICATION AND LISTING OF HAZARDOUS WASTE

        1. The authority citation for part 261 continues to read as follows:

        Authority: 42 U.S.C. 6905, 6912(a), 6921, 6922, and 6938.

§ 261.3 [Amended]
        2. In § 261.3(c)(2)(ii)(8), line 3 is amended by replacing "by § 261.6(a)(3) (v) through (ix)" with "by
§ 261.6(a)(3) (v) through (viii)".

§ 261.6 [Amended]

        3. In § 261.6(a)(2), line 4, the letter "G" is amended to read "H". The entire line should now read
as: "subparts C through H of part 266 of".

        4. In § 261.6(a)(2)(ii), line 5, the reference to "subpart D" should be replaced by "subpart H".

        For the reasons set out in the preamble, 40 CFR part 265 is amended as follows:

PART 265-INTERIM STATUS STANDARDS FOR OWNERS AND OPERATORS OF HAZARDOUS
WASTE TREATMENT, STORAGE, AND DISPOSAL FACILITIES

        1. The authority citation for part 265 continues to read as follows:

        Authority: 42 U.S.C. 6905, 6912(a), 6924, 6925, 6935.

§ 265.370 [Amended]

       2. § 265.370 is amended by deleting the period (.) at the end and replacing it with the following: ",
and subpart H of part 266, if the unit is a boiler or an industrial furnace as defined in § 260.10."

        For the reasons set out in the preamble, 40 CFR part 270 is amended as follows:

PART 270-EPA ADMINISTERED PERMIT PROGRAMS: THE HAZARDOUS WASTE PERMIT
PROGRAM

        1. The authority citation for part 270 continues to read as follows:

        Authority: 42 U.S.C. 6905, 6912, 6924, 6925, 6927, 6939, 6974.

§ 270.1 [Amended]

        2. § 270.1(b) is amended by replacing "40 CFR part 265" in line 44 by "40 CFR parts 265 and
266".

§ 270.42 [Amended]

        3. Section 270.42(c)(1)(iv) is revised to read as follows:

        (c) * * *

        (1) * * *

        (iv) Provides the applicable information required by 40 CFR 270.13 through 270.22, 270.62,
270.63, and 270.66.

*       *           *    *        *

        For the reasons set out in the preamble, 40 CFR part 266 is amended as follows:

PART 266-STANDARDS FOR THE MANAGEMENT OF SPECIFIC HAZARDOUS WASTES AND
SPECIFIC TYPES OF HAZARDOUS WASTE MANAGEMENT FACILITIES
        1. The authority citation for part 266 continues to read as follows:

        Authority: Secs. 1006, 2002(a), 3004, and 3014 of the Solid Waste Disposal Act, as amended (42
U.S.C. 6905, 6912(a), 6924, and 6934).

§ 266.4 [Amended]

        2. Section 266.40(c) is amended by replacing "subpart D" in line 6 by "subpart H."

        3. Section 266.40(d) is amended by replacing "subpart D" in line 4 by "subpart H".

        4. Part 266 is amended by adding two appendices, appendices IX and X as follows:

Appendix IX to Part 266-Methods Manual for Compliance With the BIF Regulations

Burning Hazardous Waste in Boilers and Industrial Furnaces

Table of Contents

1.0 Introduction

2.0 Performance Specifications for Continuous Emission Monitoring Systems

2.1 Performance Specifications for Continuous Emission Monitoring of Carbon Monoxide and Oxygen for
Incinerators, Boilers, and industrial Furnaces Burning Hazardous Waste

2.2 Performance Specifications for Continuous Emission Monitoring of Hydrocarbons for Incinerators,
Boilers, and Industrial Furnaces

3.0 Sampling and Analytical Methods

3.1 Methodology for the Determination of Metals Emissions in Exhaust Gases from Hazardous Waste
Incineration and Similar Combustion Processes
                                                                                             +6
3.2 Determination of Hexavalent Chromium Emissions from Stationary Sources (Method Cr )

3.3 Measurement of HCl and Cl2

3.3.1 Isokinetic HCl/Cl2 Emission Sampling Train (Method 0050)

3.3.2 Midget Impinger HCl/Cl2 Emission Sampling Train (Method 0051)

3.3.3 Protocol for Analysis of Samples from HCl/Cl2 Emission Sampling Train (Method 9057)

3.4 Determination of Polychlorinated Dibenzo-p-Dioxins (PCDDs) and Polychlorinated Dibenzofurans
(PCDFs) from Stationary Sources (Method 23)

3.5 Sampling for Aldehyde and Ketone Emissions from Stationary Sources (Method 0011)

3.6 Analysis for Aldehydes and Ketones by High Performance Liquid Chromatography (HPLC) (Method
0011A)

4.0 Procedure for Estimating Toxicity Equipment or Chlorinated Dibenzo-P-Dioxin and Dibenzofuran
Congeners

5.0 Hazardous Waste Combustion Air Quality Screening Procedure
6.0 Simplified Land Use Classification Procedure for Compliance With Tier I and Tier II Limits

7.0 Statistical Methodology for Bevill Residue Determinations

8.0 Procedures for Determining Default Values for Air Pollution Control System Removal Efficiencies

8.1 APCS RE Default Values for Metals

8.2 APCS RE Default Values for HCl and Cl2

8.3 APCS RE Default Values for Ash

8.4 References

9.0 Procedures for Determining Default Values for Partitioning of Metals, Ash, and Total Chloride/Chlorine

9.1 Partitioning Default Value for Metals

9.2 Special Procedures for Chlorine, HCl, and Cl,

9.3 Special Procedures for Ash

9.4 Use of Engineering Judgement to Estimate Partitioning and APCS RE Values

9.5 Restrictions on Use of Test Data

10.0 Alternate Methodology for Implementing Metals Controls

10.1 Applicability

10.2 Introduction

10.3 Basis

10.4 Overviev

10.5 Implementation Procedures

10.6 Precompliance Procedures

Appendix A-Statistics

Section 1.0 INTRODUCTION

        This document presents required methods for demonstrating compliance uith U.S. Environmental
Protection Agency regulations for boilers and industrial furnaces (BIFs) burning hazardous waste (see 40
CFR part 266, subpart H). Included in this document are:

       1. Performance Specifications for Continuous Emission Monitoring (CEM) of Carbon Monoxide,
Oxygen, and Hydrocarbons in Stack Gases.

        2. Sampling and Analytical (S&A) Methods for Multiple Metals, Hexavalent Chromium, HCl and
Chlorine, Polychlorinated Dibenzo-p-dioxins and Dibenzofurans, and Aldehydes and Ketones.
       3. Procedures for Estimating the Toxicity Equivalency of Chlorinated Dibenzo-p-dioxin and
Dibenzofuran Congeners.

        4. Hazardous Waste Combustion Air Quality Screening Procedures (HWCAQSP).

        5. Simplified Land Use Classification Procedure for Compliance vith Tier I and Tier II Limits.

        6. Statistical Methodology for Bevill Residue Determinations.

         7. Procedures for Determining Default Values for Air Pollution Control System Removal
Efficiencies.

        8. Procedures for Determining Default Values for Partitioning of Metals, Ash, and Total
Chloride/Chlorine.

        9. Alternate Methodology for Implementing Metals Controls.

        Additional methods referenced in subpart H of part 266 but not included in this document can be
found in 40 CFR parts 60 and 61, and "Test Methods for Evaluating Solid Wastes, Physical/Chemical
Methods" (SW-846).

         The CEM performance specifications of section 2.0, the S&A methods of section 3.0 and the
toxicity equivalency procedure for dioxins and furans of section 4.0 are required procedures for
determining compliance with BIF regulations. The CEM performance specifications and the S&A methods
are interim. The finalized CEM performance specifications and methods will be published in SW-846 or
40 CFR parts 60 and 6l.

SECTION 2.0 PERFORMANCE SPECIFICATIONS FOR CONTINUOUS EMISSION MONITORING
SYSTEMS

2.l Performance Specifications for Continuous Emission Monitoring of Carbon Monoxide and Oxygen for
Incinerators, Boilers, and Industrial Furnaces Burning Hazardous Waste

2.1.1 Applicability and Principle

         2.1.1.1 Applicability. These performance specifications apply to carbon monoxide (CO) and
oxygen (O2) continuous emission monitoring systems (CEMSs) installed on incinerators, boilers, and
industrial furnaces burning hazardous waste. The specifications include procedures which are intended to
be used to evaluate the acceptability of the CEMS at the time of its installation or whenever specified in
regulations or permits. The procedures are not designed to evaluate CEMS performance over an
extended period of time. The source owner or operator is responsible for the proper calibration,
maintenance, and operation of the CEMS at all times.

        2.1.1.2 Principle. Installation and measurement location specifications, performance and
equipment specifications, test and data reduction procedures, and brief quality assurance guidelines are
included in the specifications. Calibration drift, relative accuracy, calibration error, and response time tests
are conducted to determine conformance of the CEMS with the specifications.

2.1.2 Definitions

        2.1.2.1 Continuous Emission Monitoring System (CEMS). A continuous monitor is one in which
the sample to be analyzed passes the measurement section of the analyzer without interruption, and
which evaluates the detector response to the sample at least once each 15 seconds and computes and
records the results at least every 60 seconds. A CEMS consists of all the equipment used to acquire data
and includes the sample extraction and transport hardware, the analyzer(s), and the data
recording/processing hardware and software.
         2.1.2.2 Monitoring System Types. The specifications require CEMSs capable of accepting
calibration gases. Alternative system designs may be used if approved by the Regional Administrator.
There are two basic types of monitoring systems: extractive and in-situ.

       2.1.2.2.1 Extractive. Systems that use a pump or other mechanical, pneumatic, or hydraulic
means to draw a sample of the stack or flue gas and convey it to a remotely located analyzer.

         2.1.2.2.2 In-situ. Systems that perform an analysis without removing a sample from the stack.
Point in-situ analyzers place the sensing or detecting element directly in the flue gas stream. Cross-stack
in-situ analyzers measure the parameter of interest by placing a source beam on one side of the stack
and the detector (in single-pass instruments) or a retroreflector (in double-pass instruments) on the other
side, and measuring the parameter of interest (e.g., CO) by the attenuation of the beam by the gas in its
path.

        2.1.2.3 Instrument Measurement Range. The difference between the minimum and maximum
concentration that can be measured by a specific instrument. The minimum is often stated or assumed to
be zero and the range expressed only as the maximum.

        2.1.2.4 Span or Span Value. Full scale instrument measurement range.

        2.1.2.5 Calibration Drift (CD). The difference in the CEMS output readings from the established
reference value after a stated period of operation during which no unscheduled maintenance, repair, or
adjustment takes place. A CD test is performed to demonstrate the stability of the CEMS calibration over
time.

         2.1.2.6 Response Time. The time interval between the start of a step change in the system input
(e.g., change of calibration gas) and the time when the data recorder displays 95 percent of the final
value.

        2.1.2.7 Accuracy. A measure of agreement between a measured value and an accepted or true
value, expressed as the percentage difference between the true and measured values relative to the true
value. For these performance specifications, accuracy is checked by conducting a calibration error (CE)
test and a relative accuracy (RA) test. Certain facilities, such as those using solid waste or batch-fed
processes, may observe long periods of almost no CO emissions with brief, high-level CO emission
spikes. These facilities, as well as facilities whose CO emissions never exceed 5-10 ppm, may need to be
exempted from the RA requirement because the RA test procedure cannot ensure acquisition of
meaningful test results under these conditions. An alternative procedure for accuracy determination is
described in section 2.1.9.

        2.1.2.8 Calibration Error (CE). The difference between the concentration indicated by the CEMS
and the known concentration of the cylinder gas. A CE test procedure is performed to document the
accuracy and linearity of the monitoring equipment over the entire measurement range.

          2.1.2.9 Relative Accuracy (RA). A comparison of the CEMS response to a value measured by a
performance test method (PTM). The PA test is used to validate the calibration technique and verify the
ability of the CEMS to provide representative and accurate measurements.

        2.1.2.10 Performance Test Method (PTM). The sampling and analysis procedure used to obtain
reference measurements for comparison to CEMS measurements. The applicable test methods are
                                                                                                   2
Method 10, 10A, or 10B (for the determination of CO) and Method 3 or 3A (for the determination of 0 ).
These methods are found in 40 CFR part 60, appendix A.

       2.1.2.11 Performance Specification Test (PST) Period. The period during which CD, CE,
response time, and RA tests are conducted.
        2.1.2.12 Centroidal Area. A concentric area that is geometrically similar to the stack or duct cross
section and is no greater than 1 percent of the stack or duct cross-sectional area.

2.1.3 Installation and Measurement Location Specifications

         2.1.3.1 CEMS Installation and Measurement Locations. The CEMS shall be installed in a location
in which measurements representative of the source's emissions can be obtained. The optimum location
of the sample interface for the CEMS is determined by a number of factors, including ease of access for
calibration and maintenance, the degree to which sample conditioning will be required, the degree to
which it represents total emissions, and the degree to which it represents the combustion situation in the
firebox. The location should be as free from in-leakage influences as possible and reasonably free from
severe flow disturbances. The sample location should be at least two equivalent duct diameters
downstream from the nearest control device, point of pollutant generation, or other point at which a
change in the pollutant concentration or emission rate occurs and at least 0.5 diameter upstream from the
exhaust or control device. The equivalent duct diameter is calculated as per 40 CFR part 60, appendix A,
method 1, section 2.1. If these criteria are not achievable or if the location is otherwise less than optimum,
the possibility of stratification should be checked as described in Section 2.1.3.3 to determine whether the
location would cause failure of the relative accuracy test.

         2.1.3.1.1 For extractive or point in-situ CEMSs, the measurement point should be within or
centrally located over the centroidal area of the stack or duct cross section.

        2.1.3.1.2 For cross-stack CEMSs, the effective measurement path should (1) have at least 70
percent of the path within the inner 50 percent of the stack or duct cross-sectional area or (2) be centrally
located over any part of the centroidal area.

         2.1.3.1.3 Both the CO and O2 monitors should be installed at the same general location. If this is
not possible, they may be installed at different locations if the effluent gases at both sample locations are
not stratified and there is no in-leakage of air between sampling locations.

        2.1.3.2 Performance Test Method (PTM) Measurement Location and Traverse Points.

         2.1.3.2.1 Select an accessible PTM measurement point at least two equivalent diameters
downstream from the nearest control device, the point of CO generation, or other point at which a change
in the CO concentration may occur, and at least a half equivalent diameter upstream from the effluent
exhaust or control device. When pollutant concentration changes are due solely to diluent leakage (e.g.,
air heater leakages) and CO and O2 are simultaneously measured at the same location, one half diameter
may be used in place of two equivalent diameters. The CEMS and PTM locations need not be the same.

           2.1.3.2.2 Select traverse points that ensure acquisition of representative samples over the stack
or duct cross section. At a minimum, establish a measurement line that passes through the centroidal
area in the direction of any expected stratification. If this line interferes with the CEMS measurements,
displace the line up to 30 cm (or 5 percent of the equivalent diameter of the cross section, whichever is
less) from the centroidal area. Locate three traverse points at 17, 50, and 83 percent of the measurement
line. If the measurement line is no longer than 2.4 meters and pollutant stratification is not expected, the
tester may choose to locate the three traverse points on the line at 0.4, 1.2, and 2.0 meters from the stack
or duct wall. This option must not be used at a site located within eight equivalent diameters downstream
of a flow disturbance. The tester may select other traverse points, provided that they can be shown to the
satisfaction of the Administrator to provide a representative sample over the stack or duct cross-section.
Conduct all necessary PTM tests within 3 cm of the selected traverse points. Sampling must not be
performed within 3 cm of the duct or stack inner wall.

        2.1.3.3 Stratification Test Procedure. Stratification is defined as a difference in excess of 10
percent between the average concentration in the duct or stack and the concentration at any point more
than 1.0 meter from the duct or stack wall. To determine whether effluent stratification exists, a dual probe
system should be used to determine the average effluent concentration while measurements at each
traverse point are being made. One probe, located at the stack or duct centroid, is used as a stationary
reference point to indicate the change in effluent concentration over time. The second probe is used for
sampling at the traverse points specified in method 1, appendix A, 40 CFR part 60. The monitoring
system samples sequentially at the reference and traverse points throughout the testing period for five
minutes at each point.

            2.1.4 CEMS Performance and Equipment Specifications

         Table 2.1-1 summarizes the performance specifications for the CEMSs. Two sets of standards for
CO are given; one for low-range and another for high-range measurements. The high-range
specifications relate to measurement and quantification of short duration high concentration peaks, while
the low-range specifications relate to the overall average operating condition of the burning device. The
dual-range specifications can be met by using (1) one analyzer for each range, (2) a dual range unit, or
(3) a single measurement range instrument capable of meeting both specifications with a single unit.
Adjustments cannot be made to the analyzer between determinations of low- and high-level accuracy
within the single measurement range. In the second case, when the concentration exceeds the span of
the lower range, the data acquisition system recorder shall switch to the high range automatically.

         2.1.4.1 CEMS Span Value. In order to measure high and low concentrations with the same or
similar degree of accuracy, the maximum ranges (span values) are specified for low and high range
analyzers. The span values are listed in Table 2.1-2. Tier I and Tier II format definitions are established in
40 CFR part 266, subpart H.

Table 2.1-1-Performance Specifications of CO and O2 Monitors



                                  CO monitors


    Parameter                     Low range                High range                   O2 monitors



                                          1
    Calibration drift 24 hours.   6 ppm                  90 ppm                     0.5% O2
                                              1
    Calibration error.            10 ppm                 150 ppm                    0.5% O2

    Response time.                2 min                  2 min                      2 min
                         2         3                       3
    Relative accuracy .           ()                       ()                           (incorporated in CO RA
                                                                                        calculation)



1
  For Tier II, CD and CE are 3% and 5% of twice the permit limit, respectively.
2
  Expressed as the sum of the mean absolute value plus the 95% confidence interval of a series of measurements.
3
  The greater of 10% of PTM or 10 ppm.

Table 2.1-2-CEMS Span Values for CO and O2 Monitors



                                  CO monitors


                                  Low range (ppm)          High range (ppm)             O2 monitors (percent)
Tier I rolling average       200                         3,000                        25
format.
Tier II rolling average      2 X permit limit.           3,000                        25
format.




         2.1.4.2 Daily Calibration Gas Values. The owner or operator must choose calibration gas
concentrations (or calibration filters for in-situ systems) that include zero and high-level calibration values
for the daily calibration checks. For a single measurement range monitor, three CO calibration gas
concentrations (or calibration filters for in-situ systems) shall be used, i.e., the zero and high-level
concentrations of the low-range CO analyzer and the high-level concentration of the high-range CO
analyzer.

        2.1.4.2.1 The zero level for the CO or O2 analyzer may be between zero and 20 percent of the
span value, e.g., 0-40 ppm for low-range CO analyzer, 0-600 ppm for the high-range CO analyzer, and
0-5 percent for the O2 analyzer (for Tier I).

        2.1.4.2.2 The high-level concentration for the CO or O 2 analyzer shall be between 50 and 90
percent of the span value, i.e., 100-180 ppm for the low-range CO analyzer, 1500-2700 ppm for the
high-range CO analyzer, and 12.5-22.5 percent O2 for the O2 analyzer.

        2.1.4.3 Data Recorder Scale. The strip chart recorder, computer, or digital recorder must be
capable of recording all readings within the CEMS's measurement range and shall have a resolution of
0.5 percent of span value, i.e., 1 ppm CO for low-range CO analyzer, 15 ppm CO for high-range CO
analyzer, and 0.1 percent O2 for the O2 analyzer.

        2.1.4.4 Response Time. The response time for the CO or O2 monitor shall not exceed 2 minutes
to achieve 95 percent of the final stable value.

         2.1.4.5 Calibration Drift. The CEMS must allow the determination of CD at the zero and high-level
values. The CD must be determined separately for CO and O2 monitors in terms of concentration. The
CO CEMS calibration response must not drift or deviate from the reference value of the calibration gas (or
calibration filters for in-situ systems) by more than 3 percent of the span value after each 24-hour period
of the 7-day test, i.e., 6 ppm CO for the low-range analyzer (Tier I) and 90 ppm for the high-range
analyzer, at both zero and high levels. The O2 monitor calibration response must not drift or deviate from
the reference value by more than 0.5 percent O2 at both zero and high levels.

        2.l.4.6 Relative Accuracy. The result of the PA test of the CO CEMS (which incorporates the O 2
monitor) must be no greater than 10 percent of the mean value of the PTM results or must be within 10
ppm CO of the PTM results, whichever is less restrictive. The ppm CO concentration shall be corrected to
7 percent O2 before calculating the RA.

        2.1.4.7 Calibration Error. The mean difference between the CEMS and reference values at all
three test points (see Table 2.1-3) must be no greater than 5 percent of span value for CO monitors (i.e.,
10 ppm CO for low range Tier I CO analyzers and 150 ppm CO for high range CO analyzers) and 0.5
percent for O2 analyzers.

         2.1.4.8 Measurement and Recording Frequency. The sample to be analyzed shall pass through
the measurement section of the analyzer without interruption. The detector shall measure the sample
concentration at least once every 15 seconds. An average emission rate shall be computed and recorded
at least once every 60 seconds.

         2.1.4.9 Hourly Rolling Average Calculation. The CEMS shall calculate every minute an hourly
rolling average, which is the arithmetic mean of the 60 most recent 1-minute average values.
         2.1.4.10 Retest. If the CEMS produces results within the specified criteria, the test is successful.
If the CEMS does not meet one or more of the criteria, the necessary corrections must be made and the
performance tests repeated.

2.1.5 Test Periods

        2.1.5.1 Pretest Preparation Period. Install the CEMS, prepare the PTM test site according to the
specifications in section 2.1.3, and prepare the CEMS for operation and calibration according to the
manufacturer's written instructions. A pretest conditioning period similar to that of the 7-day CD test is
recommended to verify the operational status of the CEMS.

        2.1.5.2 Calibration Drift Test Period. While the facility is operating under normal conditions,
determine the CD at 24-hour intervals for seven consecutive days according to the procedure given in
section 2.1.6.1. All CD determinations must be made following a 24-hour period during which no
unscheduled maintenance, repair, or adjustment takes place. If the combustion unit is taken out of service
during the test period, record the onset and duration of the downtime and continue the calibration drift test
when the unit resumes operation.

        2.1.5.3 Relative Accuracy Test Period. Conduct the RA test according to the procedure in section
2.1.6.4 while the facility is operating under normal conditions. RA testing for CO and O 2 shall be
conducted simultaneously so that the results can be calculated for CO corrected to 7 percent O 2. The RA
test shall be conducted during the CD test period. It is emphasized that during the CD test period, no
adjustments or repairs may be made to the CEMS other than routine calibration adjustments performed
immediately following the daily CD determination.

        2.1.5.4 Calibration Error Test and Response Time Test Periods. Conduct the CE and response
time tests during the CD test period.

2.1.6 Performance Specification Test Procedures

        2.1.6.1 Calibration Drift Test.

         2.1.6.1.1 Sampling Strategy. Conduct the CD test for all monitors at 24-hour intervals for seven
consecutive days using calibration gases at the two (or three, if applicable) concentration levels specified
in section 2.1.4.2. Introduce the calibration gases into the sampling system as close to the sampling
probe outlet as practical. The gas shall pass through all filters, scrubbers, conditioners, and other CEMS
components used during normal sampling. If periodic automatic or manual adjustments are made to the
CEMS zero and calibration settings, conduct the CD test immediately before these adjustments, or
conduct it in such a way that the CD can be determined. Record the CEMS response and subtract this
value from the reference (calibration gas) value. To meet the specification, none of the differences shall
exceed the limits specified in Table 2.1-1.

        2.1.6.1.2 Calculations. Summarize the results on a data sheet. An example is shown in Figure
2.1-1. Calculate the differences between the CEMS responses and the reference values.

       2.1.6.2 Response Time. Check the entire CEMS including sample extraction and transport,
sample conditioning, gas analyses, and the data recording.

         2.1.6.2.1 Introduce zero gas into the system. For extractive systems, introduce the calibration
gases at the probe as near to the sample location as possible. For in-situ system, introduce the zero gas
at a point such that all components active in the analysis are tested. When the system output has
stabilized (no change greater than 1 percent of full scale for 30 seconds), switch to monitor stack effluent
and wait for a stable value. Record the time (upscale response time) required to reach 95 percent of the
final stable value.
         2.1.6.2.2 Next, introduce a high-level calibration gas and repeat the above procedure. Repeat the
entire procedure three times and determine the mean upscale and downscale response times. The longer
of the two means is the system response time.

           2.1.6.3 Calibration Error Test Procedure.

        2.1.6.3.1 Sampling Strategy. Challenge each monitor (both low- and high-range CO and O2) with
zero gas and EPA Protocol 1 cylinder gases at three measurement points within the ranges specified in
Table 2.1-3.

Table 2.1-3-Calibration Error Concentration Ranges for Tier I



                             GAS Concentration Ranges


                             CO, ppm

                                          1
    Measurement point         Low range                     High range                  O2
                                                                                        percent



    1                         0-40                          0-600                       0-2
    2                         60-80                         900-1200                    8-10
    3                         140-160                       2100-2400                   14-16



1
  For Tier II, the CE specifications for the low-range CO CEMS are 0-20%, 30-40%, and 70-80% of twice the permit
limit.

>>>> See the accompanying hardcopy volume for non-machine-readable data that appears at this point.
<<<<

        2.1.6.3.1.1 If a single measurement range is used, the calibration gases used in the daily CD
checks (if they are Protocol 1 cylinder gases and meet the criteria in section 2.1.6.3.1) may be used for
determining CE.

         2.1.6.3.1.2 Operate each monitor in its normal sampling mode as nearly as possible. The
calibration gas shall be injected into the sample system as close to the sampling probe outlet as practical
and should pass through all CEMS components used during normal sampling. Challenge the CEMS three
non-consecutive times at each measurement point and record the responses. The duration of each gas
injection should be sufficient to ensure that the CEMS surfaces are conditioned.

         2.1.6.3.2 Calculations. Summarize the results on a data sheet. An example data sheet is shown
in Figure 2.1-2. Average the differences between the instrument response and the certified cylinder gas
value for each gas. Calculate three CE results (five CE results for a single-range CO CEMS) according to
Equation 5 (section 2.1.7.5). No confidence coefficient is used in CE calculations.

           2.1.6.4 Relative Accuracy Test Procedure.

         2.1.6.4.1 Sampling Strategy for PTM tests. Conduct the PTM tests in such a way that they will
yield measurements representative of the emissions from the source and can be correlated to the CEMS
data. Although it is preferable to conduct the CO, diluent, and moisture (if needed) simultaneously,
moisture measurements that are taken within a 60-minute period which includes the simultaneous CO
and O2 measurements may be used to calculate the dry CO concentration.

         Note: At times, CEMS RA tests may be conducted during incinerator performance tests. In these
cases, PTM results obtained during CEMS RA tests may be used to determine compliance with
incinerator emissions limits as long as the source and test conditions are consistent with the applicable
regulations.

>>>> See the accompanying hardcopy volume for non-machine-readable data that appears at this point.
<<<<

        2.1.6.4.2 Performance Test Methods.

        2.1.6.4.2.1 Unless otherwise specified in the regulations, method 3 or 3A and method 10, 10A, or
10B (40 CFR part 60, appendix A) are the test methods for O2 and CO, respectively. Make a sample
traverse of at least 21 minutes, sampling for 7 minutes at each of three traverse points (see section 3.2).

         2.1.6.4.2.2 When the installed CEMS uses a nondispersive infrared (NDIR) analyzer, method 10
shall use the alternative interference trap specified in section 10.1 of the method. An option, which may
be approved by the Administrator in certain cases, would allow the test to be conducted using method 10
without the interference trap. Under this option, a laboratory interference test is performed for the
analyzer prior to the field test. The laboratory interference test includes the analysis of SO 2, NO, and CO2
calibration gases over the range of expected effluent concentrations. Acceptable performance is indicated
if the CO analyzer response to each of the gases is less than 1 percent of the applicable measurement
range of the analyzer.

        2.1.6.4.3 Number of PTM Tests. Conduct a minimum of nine sets of all necessary PTM tests. If
more than nine sets are conducted, a maximum of three sets may be rejected at the tester's discretion.
The total number of sets used to determine the RA must be greater than or equal to nine. All data,
including the rejected data, must be reported.

         2.1.6.4.4 Correlation of PTM and CEMS Data. The time and duration of each PTM test run and
the CEMS response time should be considered in correlating the data. Use the CEMS final output (the
one used for reporting) to determine an integrated average CO concentration for each PTM test run.
Confirm that the pair of results are on a consistent moisture and O 2 concentration basis. Each integrated
CEMS value should then be compared against the corresponding average PTM value. If the CO
concentration measured by the CEMS is normalized to a specified diluent concentration, the PTM results
shall be normalized to the same value.

         2.1.6.4.5 Calculations. Summarize the results on a data sheet. Calculate the mean of the PTM
values and calculate the arithmetic differences between the PTM and the CEMS data sets. The mean of
the differences, standard deviation, confidence coefficient, and CEMS RA should be calculated using
Equations 1 through 4.

2.1.7 Equations

        2.1.7.1 Arithmetic Mean (). Calculate ,  of the difference of a data set using Equation 1.

>>>> See the accompanying hardcopy volume for non-machine-readable data that appears at this point.
<<<<

where: n = Number of data points.

n

        di = Algebraic sum of the individual difference di.


i=1


        When the mean of the differences of pairs of data is calculated, correct the data for moisture, if
applicable.

            2.1.7.2 Standard Deviation (Sd). Calculate Sd using Equation 2.

>>>> See the accompanying hardcopy volume for non-machine-readable data that appears at this point.
<<<<

       2.1.7.3 Confidence Coefficient (CC). Calculate the 2.5 percent error CC (one-tailed) using
Equation 3.

>>>> See the accompanying hardcopy volume for non-machine-readable data that appears at this point.
<<<<

where:

t0.975 = t-value (see Table 2.1-4).

Table 2.1-4-t-Values



        a                                    a                                    a
    n                  t0.975            n                   t0.975           n              t0.975



    2                  12.706            7                   2.447            12             2.201
    3                  4.303             8                   2.365            13             2.179
    4                  3.182             9                   2.306            14             2.160
    5                  2.776             10                  2.662            15             2.145
    6                  2.571             11                  2.228            16             2.131



a
 The values in this table are already corrected for n-1 degrees of freedom.
Use n equal to the number of individual values.


            2.1.7.4 Relative Accuracy. Calculate the RA of a set of data using Equation 4.

>>>> See the accompanying hardcopy volume for non-machine-readable data that appears at this point.
<<<<

where:

=          Absolute value of the mean of the differences (Equation 1).
CC =        Absolute value of the confidence coefficient (Equation 3).

PTM = Average reference value.

            2.1.7.5 Calibration Error. Calculate CE using Equation 5.
>>>> See the accompanying hardcopy volume for non-machine-readable data that appears at this point.
<<<<

where:

 = Mean difference between CEMS response and the known reference concentration.

2.1.8 Reporting

        At a minimum, summarize in tabular form the results of the CD, RA, response time, and CE test,
as appropriate. Include all data sheets, calculations, CEMS data records, and cylinder gas or reference
material certifications.

2.1.9 Alternative Procedure

         2.1.9.1 Alternative RA Procedure Rationale. Under some operating conditions, it may not be
possible to obtain meaningful results using the RA test procedure. This includes conditions where
consistent, very low CO emissions or low CO emissions interrupted periodically by short duration, high
level spikes are observed. It may be appropriate in these circumstances to waive the PTM RA test and
substitute the following procedure.

        2.1.9.2 Alternative RA Procedure. Conduct a complete CEMS status check following the
manufacturer's written instructions. The check should include operation of the light source, signal
receiver, timing mechanism functions, data acquisition and data reduction functions, data recorders,
mechanically operated functions (mirror movements, calibration gas valve operations, etc.), sample filters,
sample line heaters, moisture traps, and other related functions of the CEMS, as applicable. All parts of
the CEMS must be functioning properly before the RA requirement can be waived. The instruments must
also have successfully passed the CE and CD requirements of the performance specifications.
Substitution of the alternative procedure requires approval of the Regional Administrator.

2.1.10 Quality Assurance (QA)

        Proper calibration, maintenance, and operation of the CEMS is the responsibility of the owner or
operator. The owner or operator must establish a QA program to evaluate and monitor CEMS
performance. As a minimum, the QA program must include:

         2.1.10.1 A daily calibration check for each monitor. The calibration must be adjusted if the check
indicates the instrument's CD exceeds the specification established in section 2.1.4.5. The gases shall be
injected as close to the probe as possible to provide a check of the entire sampling system. If an
alternative calibration procedure is desired (e.g., direct injections or gas cells), subject to Administrator
approval, the adequacy of this alternative procedure may be demonstrated during the initial 7-day CD
test. Periodic comparisons of the two procedures are suggested.

        2.1.10.2 A daily system audit. The audit must include a review of the calibration check data, an
inspection of the recording system, an inspection of the control panel warning lights, and an inspection of
the sample transport and interface system (e.g., flowmeters, filters), as appropriate.

        2.1.10.3 A quarterly calibration error (CE) test. Quarterly RA tests may be substituted for the CE
test when approved by the Director on a case-by-case basis.

         2.1.10.4 An annual performance specification test.

2.1.11 References
       1. Jahnke, James A. and G.J. Aldina, "Handbook: Continuous Air Pollution Source Monitoring
Systems," U.S. Environmental Protection Agency Technology Transfer, Cincinnati, Ohio 45268,
EPA-625/6-79-005, June 1979.

       2. "Gaseous Continuous Emissions Monitoring Systems-Performance Specification Guidelines for
SO2, NOx, CO2, O2, and TRS." U.S. Environmental Protection Agency OAQPS, ESED, Research Triangle
Park, North Carolina 27711, EPA-450/3-82-026, October 1982.

       3. "Quality Assurance Handbook for Air Pollution Measurement Systems: Volume I. Principles."
U.S. Environmental Protection Agency ORD/EMSL, Research Triangle Park, North Carolina, 27711,
EPA-600/9-76-006, December 1984.

       4. Michie, Raymond, M. Jr., et. al., "Performance Test Results and Comparative Data for
Designated Reference Methods for Carbon Monoxide," U.S. Environmental Protection Agency
ORD/EMSL, Research Triangle Park, North Carolina, 27711, EPA-600/S4-83-013, September 1982.

       5. Ferguson, B.B., R.E. Lester, and W.J. Mitchell, "Field Evaluation of Carbon Monoxide and
Hydrogen Sulfide Continuous Emission Monitors at an Oil Refinery," U.S. Environmental Protection
Agency, Research Triangle Park, North Carolina, 27711, EPA-600/4-82-054, August 1982.

2.2 Performance Specifications for Continuous Emission Monitoring of Hydrocarbons for Incinerators,
Boilers, and Industrial Furnaces Burning Hazardous Waste

2.2.1 Applicability and Principle

        2.2.1.1 Applicability. These performance specifications apply to hydrocarbon (HC) continuous
emission monitoring systems (CEMSs) installed on incinerators, boilers, and industrial furnaces burning
hazardous waste. The specifications include procedures which are intended to be used to evaluate the
acceptability of the CEMS at the time of its installation or whenever specified in regulations or permits.
The procedures are not designed to evaluate CEMS performance over an extended period of time. The
source owner or operator is responsible for the proper calibration, maintenance, and operation of the
CEMS at all times.

         2.2.1.2 Principle. A gas sample is extracted from the source through a heated sample line and
heated filter (except as provided by section 2.2.10) to a flame ionization detector (FID). Results are
reported as volume concentration equivalents of propane. Installation and measurement location
specifications, performance and equipment specifications, test and data reduction procedures, and brief
quality assurance guidelines are included in the specifications. Calibration drift, calibration error, and
response time tests are conducted to determine conformance of the CEMS with the specifications.

2.2.2 Definitions

        2.2.2.1 Continuous Emission Monitoring System (CEMS). The total equipment used to acquire
data, which includes sample extraction and transport hardware, analyzer, data recording and processing
hardware, and software. The system consists of the following major subsystems:

         2.2.2.1.1 Sample Interface. That portion of the system that is used for one or more of the
following: Sample acquisition, sample transportation, sample conditioning, or protection of the analyzer
from the effects of the stack effluent.

       2.2.2.1.2 Organic Analyzer. That portion of the system that senses organic concentration and
generates an output proportional to the gas concentration.

      2.2.2.1.3 Data Recorder. That portion of the system that records a permanent record of the
measurement values. The data recorder may include automatic data reduction capabilities.
        2.2.2.2 Instrument Measurement Range. The difference between the minimum and maximum
concentration that can be measured by a specific instrument. The minimum is often stated or assumed to
be zero and the range expressed only as the maximum.

        2.2.2.3 Span or Span Value. Full scale instrument measurement range.

        2.2.2.4 Calibration Gas. A known concentration of a gas in an appropriate diluent gas.

        2.2.2.5 Calibration Drift (CD). The difference in the CEMS output readings from the established
reference value after a stated period of operation during which no unscheduled maintenance, repair, or
adjustment takes place. A CD test is performed to demonstrate the stability of the CEMS calibration over
time.

         2.2.2.6 Response Time. The time interval between the start of a step change in the system input
(e.g., change of calibration gas) and the time when the data recorder displays 95 percent of the final
value.

         2.2.2.7 Accuracy. A measurement of agreement between a measured value and an accepted or
true value, expressed as the percentage difference between the true and measured values relative to the
true value. For these performance specifications, accuracy is checked by conducting a calibration error
(CE) test.

        2.2.2.8 Calibration Error (CE). The difference between the concentration indicated by the CEMS
and the known concentration of the cylinder gas. A CE test procedure is performed to document the
accuracy and linearity of the monitoring equipment over the entire measurement range.

       2.2.2.9 Performance Specification Test (PST) Period. The period during which CD, CE, and
response time tests are conducted.

        2.2.2.10 Centroidal Area. A concentric area that is geometrically similar to the stack or duct cross
section and is no greater than 1 percent of the stack or duct cross-sectional area.

2.2.3 Installation and Measurement Location Specifications

         2.2.3.1 CEMS Installation and Measurement Locations. The CEMS shall be installed in a location
in which measurements representative of the source's emissions can be obtained. The optimum location
of the sample interface for the CEMS is determined by a number of factors, including ease of access for
calibration and maintenance, the degree to which sample conditioning will be required, the degree to
which it represents total emissions, and the degree to which it represents the combustion situation in the
firebox. The location should be as free from in-leakage influences as possible and reasonably free from
severe flow disturbances. The sample location should be at least two equivalent duct diameters
downstream from the nearest control device, point of pollutant generation, or other point at which a
change in the pollutant concentration or emission rate occurs and at least 0.5 diameter upstream from the
exhaust or control device. The equivalent duct diameter is calculated as per 40 CFR part 60, appendix A,
method 1, section 2.1. If these criteria are not achievable or if the location is otherwise less than optimum,
the possibility of stratification should be investigated as described in section 2.2.3.2. The measurement
point shall be within the centroidal area of the stack or duct cross section.

        2.2.3.2 Stratification Test Procedure. Stratification is defined as a difference in excess of 10
percent between the average concentration in the duct or stack and the concentration at any point more
than 1.0 meter from the duct or stack wall. To determine whether effluent stratification exists, a dual probe
system should be used to determine the average effluent concentration while measurements at each
traverse point are being made. One probe, located at the stack or duct centroid, is used as a stationary
reference point to indicate the change in effluent concentration over time. The second probe is used for
sampling at the traverse points specified in 40 CFR Part 60 appendix A, method 1. The monitoring
system samples sequentially at the reference and traverse points throughout the testing period for five
minutes at each point.

2.2.4 CEMS Performance and Equipment Specifications

        If this method is applied in highly explosive areas, caution and care shall be exercised in choice
of equipment and installation.

        2.2.4.1 Flame Ionization Detector (FID) Analyzer. A heated FID analyzer capable of meeting or
exceeding the requirements of these specifications. Heated systems shall maintain the temperature of the
sample gas between 150 C (300 F) and 175 C (350 F) throughout the system. This requires all
system components such as the probe, calibration valve, filter, sample lines, pump, and the FID to be
kept heated at all times such that no moisture is condensed out of the system.

         Note: As specified in the regulations, unheated HC CEMs may be considered an acceptable
interim alternative monitoring technique. For additional notes, see section 2.2.10. The essential
components of the measurement system are described below:

         2.2.4.1.1 Sample Probe. Stainless steel, or equivalent, to collect a gas sample from the centroidal
area of the stack cross-section.

        2.2.4.1.2 Sample Line. Stainless steel or Teflon tubing to transport the sample to the analyzer.

       Note: Mention of trade names or specific products does not constitute endorsement by the
Environmental Protection Agency.

         2.2.4.1.3 Calibration Valve Assembly. A heated three-way valve assembly to direct the zero and
calibration gases to the analyzer is recommended. Other methods, such as quick-connect lines, to route
calibration gas to the analyzers are applicable.

      2.2.4.1.4 Particulate Filter. An in-stack or out-of-stack sintered stainless steel filter is
recommended if exhaust gas particulate loading is significant. An out-of-stack filter must be heated.

        2.2.4.1.5 Fuel. The fuel specified by the manufacturer (e.g., 40 percent hydrogen/60 percent
helium, 40 percent hydrogen/60 percent nitrogen gas mixtures, or pure hydrogen) should be used.

      2.2.4.1.6 Zero Gas. High purity air with less than 0.1 parts per million by volume (ppm) HC as
methane or carbon equivalent or less than 0.1 percent of the span value, whichever is greater.

         2.2.4.1.7 Calibration Gases. Appropriate concentrations of propane gas (in air or nitrogen).
Preparation of the calibration gases should be done according to the procedures in EPA Protocol 1. In
addition, the manufacturer of the cylinder gas should provide a recommended shelf life for each
calibration gas cylinder over which the concentration does not change by more than ± 2 percent from the
certified value.

        2.2.4.2 CEMS Span Value. 100 ppm propane.

       2.2.4.3 Daily Calibration Gas Values. The owner or operator must choose calibration gas
concentrations that include zero and high-level calibration values.

        2.2.4.3.1 The zero level may be between 0 and 20 ppm (zero and 20 percent of the span value).

       2.2.4.3.2 The high-level concentration shall be between 50 and 90 ppm (50 and 90 percent of the
span value).
       2.2.4.4 Data Recorder Scale. The strip chart recorder, computer, or digital recorder must be
capable of recording all readings within the CEMS's measurement range and shall have a resolution of
0.5 ppm (0.5 percent of span value).

       2.2.4.5 Response Time. The response time for the CEMS must not exceed 2 minutes to achieve
95 percent of the final stable value.

        2.2.4.6 Calibration Drift. The CEMS must allow the determination of CD at the zero and high-level
values. The CEMS calibration response must not differ by more than ± 3 ppm (± 3 percent of the span
value) after each 24-hour period of the 7-day test at both zero and high levels.

        2.2.4.7 Calibration Error. The mean difference between the CEMS and reference values at all
three test points listed below shall be no greater than 5 ppm (± 5 percent of the span value).

        2.2.4.7.1 Zero Level. Zero to 20 ppm (0 to 20 percent of span value).

        2.2.4.7.2 Mid-Level. 30 to 40 ppm (30 to 40 percent of span value).
        2.2.4.7.3 High-Level. 70 to 80 ppm (70 to 80 percent of span value).

         2.2.4.8 Measurement and Recording Frequency. The sample to be analyzed shall pass through
the measurement section of the analyzer without interruption. The detector shall measure the sample
concentration at least once every 15 seconds. An average emission rate shall be computed and recorded
at least once every 60 seconds.

         2.2.4.9 Hourly Rolling Average Calculation. The CEMS shall calculate every minute an hourly
rolling average, which is the arithmetic mean of the 60 most recent 1-minute average values.

         2.2.4.10 Retest. If the CEMS produces results within the specified criteria, the test is successful.
If the CEMS does not meet one or more of the criteria, necessary corrections must be made and the
performance tests repeated.

2.2.5 Performance Specification Test (PST) Periods

        2.2.5.1 Pretest Preparation Period. Install the CEMS, prepare the PTM test site according to the
specifications in section 2.2.3, and prepare the CEMS for operation and calibration according to the
manufacturer's written instructions. A pretest conditioning period similar to that of the 7-day CD test is
recommended to verify the operational status of the CEMS.

         2.2.5.2 Calibration Drift Test Period. While the facility is operating under normal conditions,
determine the magnitude of the CD at 24-hour intervals for seven consecutive days according to the
procedure given in section 2.2.6.1. All CD determinations must be made following a 24-hour period during
which no unscheduled maintenance, repair, or adjustment takes place. If the combustion unit is taken out
of service during the test period, record the onset and duration of the downtime and continue the CD test
when the unit resumes operation.

        2.2.5.3 Calibration Error Test and Response Time Test Periods. Conduct the CE and response
time tests during the CD test period.

2.2.6 Performance Specification Test Procedures

        2.2.6.1 Calibration Drift Test.

         2.2.6.1.1 Sampling Strategy. Conduct the CD test at 24-hour intervals for seven consecutive days
using calibration gases at the two daily concentration levels specified in section 2.2.4.3. Introduce the two
calibration gases into the sampling system as close to the sampling probe outlet as practical. The gas
shall pass through all CEM components used during normal sampling. If periodic automatic or manual
adjustments are made to the CEMS zero and calibration settings, conduct the CD test immediately before
these adjustments, or conduct it in such a way that the CD can be determined. Record the CEMS
response and subtract this value from the reference (calibration gas) value. To meet the specification,
none of the differences shall exceed 3 ppm.

        2.2.6.1.2 Calculations. Summarize the results on a data sheet. An example is shown in Figure
2.2-1. Calculate the differences between the CEMS responses and the reference values.

        2.2.6.2 Response Time. The entire system including sample extraction and transport, sample
conditioning, gas analyses, and the data recording is checked with this procedure.

        2.2.6.2.1 Introduce the calibration gases at the probe as near to the sample location as possible.
Introduce the zero gas into the system. When the system output has stabilized (no change greater than 1
percent of full scale for 30 sec), switch to monitor stack effluent and wait for a stable value. Record the
time (upscale response time) required to reach 95 percent of the final stable value.

         2.2.6.2.2 Next, introduce a high-level calibration gas and repeat the above procedure. Repeat the
entire procedure three times and determine the mean upscale and downscale response times. The longer
of the two means is the system response time.

        2.2.6.3 Calibration Error Test Procedure.

       2.2.6.3.1 Sampling Strategy. Challenge the CEMS with zero gas and EPA Protocol 1 cylinder
gases at measurement points within the ranges specified in section 2.2.4.7.

        2.2.6.3.1.1 The daily calibration gases, if Protocol 1, may be used for this test.

>>>> See the accompanying hardcopy volume for non-machine-readable data that appears at this point.
<<<<

2.2.9 Quality Assurance (QA)

        Proper calibration, maintenance, and operation of the CEMS is the responsibility of the owner or
operator. The owner or operator must establish a QA program to evaluate and monitor CEMS
performance. As a minimum, the QA program must include:

         2.2.9.1 A daily calibration check for each monitor. The calibration must be adjusted if the check
indicates the instrument's CD exceeds 3 ppm. The gases shall be injected as close to the probe as
possible to provide a check of the entire sampling system. If an alternative calibration procedure is
desired (e.g., direct injections or gas cells), subject to Administrator approval, the adequacy of this
alternative procedure may be demonstrated during the initial 7-day CD test. Periodic comparisons of the
two procedures are suggested.

        2.2.9.2 A daily system audit. The audit must include a review of the calibration check data, an
inspection of the recording system, an inspection of the control panel warning lights, and an inspection of
the sample transport and interface system (e.g., flowmeters, filters), as appropriate.

        2.2.9.3 A quarterly CE test. Quarterly RA tests may be substituted for the CE test when approved
by the Director on a case-by-case basis.

        2.2.9.4 An annual performance specification test.

2.2.10 Alternative Measurement Technique

      The regulations allow gas conditioning systems to be used In conjunction with unheated HC
CEMs during an interim period. This gas conditioning may include cooling to not less than 40 F and the
use of condensate traps to reduce the moisture content of sample gas entering the FID to less than 2
percent. The gas conditioning system, however, must not allow the sample gas to bubble through the
condensate as this would remove water soluble organic compounds. All components upstream of the
conditioning system should be heated as described in section 2.2.4 to minimize operating and
maintenance problems.

2.2.11 References

       1. Measurement of Volatile Organic Compounds-Guideline Series. U.S. Environmental Protection
Agency, Research Triangle Park, North Carolina, 27711, EPA-450/2-78-041, June 1978.

        2. Traceability Protocol for Establishing True Concentrations of Gases Used for Calibration and
Audits of Continuous Source Emission Monitors (Protocol No. 1). U.S. Environmental Protection Agency
ORD/EMSL, Research Triangle Park, North Carolina, 27711, June 1978.

     3. Gasoline Vapor Emission Laboratory Evaluation-Part 2. U.S. Environmental Protection Agency,
OAQPS, Research Triangle Park, North Carolina, 27711, EMB Report No. 76-GAS-6, August 1975.

Section 3.0 SAMPLING AND ANALYTICAL METHODS

3.1 Methodology for the Determination of Metals Emissions in Exhaust Gases from Hazardous Waste
Incineration and Similar Combustion Processes

3.1.1 Applicability and Principle

        3.1.1.1 Applicability. This method is being developed for the determination of total chromium (Cr),
cadmium (Cd), arsenic (As), nickel (Ni), manganese (Mn), beryllium (Be), copper (Cu), zinc (Zn), lead
(Pb), selenium (Se), phosphorus (P), thallium (Tl), silver (Ag), antimony (Sb), barium (Ba), and mercury
(Hg) stack emissions from hazardous waste incinerators and similar combustion processes. This method
may also be used for the determination of particulate emissions following the procedures and precautions
described. Modifications to the sample recovery and analysis procedures described in this protocol for the
purpose of determining particulate emissions may potentially impact the front-half mercury determination.
Mercury emissions should be determined using EPA method 101A given in 40 CFR part 61.

          3.1.1.2 Principle. The stack sample is withdrawn isokinetically from the source, with particulate
emissions collected in the probe and on a heated filter and gaseous emissions collected in a series of
chilled impingers containing an aqueous solution of dilute nitric acid combined with dilute hydrogen
peroxide in each of two impingers, and acidic potassium permanganate solution in each of two impingers.
Sampling train components are recovered and digested in separate front- and back-half fractions.
Materials collected in the sampling train are digested with acid solutions to dissolve organics and to
remove organic constituents that may create analytical interferences. Acid digestion is performed using
                     ®
conventional Parr Bomb or microwave digestion techniques. The nitric acid and hydrogen peroxide
impinger solution, the acidic potassium permanganate impinger solution, the HCl rinse solution, and the
probe rinse and digested filter solutions are analyzed for mercury by cold vapor atomic absorption
spectroscopy (CVAAS). The nitric acid and hydrogen peroxide solution and the probe rinse and digested
filter solutions of the train catches are analyzed for Cr, Cd, Ni, Mn, Be, Cu, Zn, Pb, Se, P, Tl, Ag, Sb, Ba,
and As by inductively coupled argon plasma emission spectroscopy (ICAP) or atomic absorption
spectroscopy (AAS). Graphite furnace atomic absorption spectroscopy (GFAAS) is used for analysis of
antimony, arsenic, cadmium, lead, selenium, and thallium, if these elements require greater analytical
sensitivity than can be obtained by ICAP. Additionally, if desired, the tester may use AAS for analyses of
all metals if the resulting in-stack method detection limits meet the goal of the testing program. For
convenience, aliquots of each digested sample Fraction 1A plus Fraction 2A can be combined
proportionally with respect to the original Fraction 1 (normally diluted to 300 ml following digestion and
prior to analysis) section 3.1.5.3.3; and concentrated Fraction 2A (normally diluted to 150 ml following
digestion and prior to analysis) section 3.1.5.3.4.1 or 3.1.5.3.4.2 for a single analytical determination. The
efficiency of the analytical procedure is quantified by the analysis of spiked quality control samples
containing each of the target metals and/or other quality assurance measures, as necessary, including
actual sample matrix effects checks.

3.1.2 Range, Sensitivity, Precision, and Interferences

         3.1.2.1 Range. For the analyses described in this methodology and for similar analyses, the ICAP
response is linear over several orders of magnitude. Samples containing metal concentrations in the
nanograms per milliliter (ng/ml) to micrograms per milliliter (g/ml) range in the analytical finish solution
can be analyzed using this technique. Samples containing greater than approximately 50 g/ml of
chromium, lead, or arsenic should be diluted to that level or lower for final analysis. Samples containing
greater than approximately 20 g/ml of cadmium should be diluted to that level before analysis.

         3.1.2.2 Analytical Sensitivity. ICAP analytical detection limits for the sample solutions (based on
SW-846, method 6010) are approximately as follows: Sb (32 ng/ml), As (53 ng/ml), Ba (2 ng/ml), Be (0.3
ng/ml), Cd (4 ng/ml), Cr (7 ng/ml), Cu (6 ng/ml), Pb (42 ng/ml), Mn (2 ng/ml), Ni (15 ng/ml), P (75 ng/ml),
Se (75 ng/ml), Ag (7 ng/ml), T1 (40 ng/ml), and Zn (2 ng/ml). The actual method detection limits are
sample dependent and may vary as the sample matrix may affect the limits. The analytical detection limits
for analysis by direct aspiration AAS (based on SW-846, Method 7000 series) are approximately as
follows: Sb (200 ng/ml), As (2 ng/ml), Ba (100 ng/ml), Be (5 ng/ml), Cd (5 ng/ml), Cr (50 ng/ml), Cu (20
ng/ml), Pb (100 ng/ml), Mn (10 ng/ml), Ni (40 ng/ml), Se (2 ng/ml), Ag (10 ng/ml), Tl (100 ng/ml), and Zn
(5 ng/ml). The detection limit for mercury by CVAAS is approximately 0.2 ng/ml). The use of GFAAS can
give added sensitivity compared to the use of direct aspiration AAS for the following metals: Sb (3 ng/ml),
As (1 ng/ml), Be (0.2 ng/ml), Cd (0.1 ng/ml), Cr (1 ng/ml), Pb (1 ng/ml), Se (2 ng/ml), and Tl (1 ng/ml).

        Using (1) the procedures described in this method, (2) the analytical detection limits described in
the previous paragraph, (3) a volume of 300 ml, Fraction 1, for the front half and 150 ml, Fraction 2A, for
                                                                      3
the back-half samples, and (4) a stack gas sample volume of 1.25 m , the corresponding instack method
detection limits are presented in Table A-1 and calculated as shown:

                 AXB
                                  =D

                   C

where:

A = analytical detection limit, g/ml.
B = volume of sample prior to aliquot for analysis, ml.
                                       3
C = stack sample volume, dscm (dsm ).
                                   3
D = in-stack detection limit, g/m .

         Values in Table 3.1-1 are calculated for the front and back half and/or the total train.

          To ensure optimum sensitivity in obtaining the measurements, the concentrations of target metals
in the solutions are suggested to be at least ten times the analytical detection limits. Under certain
conditions, and with greater care in the analytical procedure, this concentration can be as low as
approximately three times the analytical detection limit. In all cases, on at least one sample (run) in the
source test and for each metal analyzed, repetitive analyses, method of standard additions (MSA), serial
dilution, or matrix spike addition, etc., shall be used to establish the quality of the data.

        Actual in-stack method detection limits will be determined based on actual source sampling
parameters and analytical results as described above. If required, the method in-stack detection limits can
be made more sensitive than those shown in Table A-I for a specific test by using one or more of the
following options:
                                                                                                    3
         ! A 1-hour sampling run may collect a stack gas sampling volume of about 1.25 m . If the
                                    3
sampling time is increased and 5 m are collected, the in-stack method detection limits would be one
fourth of the values shown in Table A-I (this means that with this change, the method is four times more
sensitive than a 1-hour run. Larger sample volumes (longer runs) would make it even more sensitive).

         ! The in-stack detection limits assume that all of the sample is digested (with exception of the
aliquot for mercury) and the final liquid volumes for analysis are 300 ml, Fraction 1 for the front half and
150 ml, Fraction 2A, for the back-half sample. If the front-half volume is reduced from 300 ml to 30 ml, the
front-half in-stack detection limits would be one tenth of the values shown above (ten times more
sensitive). If the back-half volume is reduced from 150 ml to 25 ml, the in-stack detection limits would be
one sixth of the above values. Matrix effects checks are necessary on analyses of samples and typically
are of greater significance for samples that have been concentrated to less than the normal original
sample volume. Reduction to a volume of less than 25 ml may not allow redissolving of the residue and
may increase interference by other compounds.

          ! When both of the above two improvements are used on one sample at the same time, the
resultant improvements are multiplicative. For example, where stack gas volume is increased by a factor
of five and the total liquid sample digested volume of both the front and back halves is reduced by a factor
of six, the in-stack method detection limit is reduced by a factor of thirty (the method is thirty times more
sensitive).

                                                          3
Table 3. 1-1-In-Stack Method Detection Limits (ug/m ) for Train Fractions Using ICAP and AAS



                                                                              Back-half        Total train
                        Front-half                                            fractions
                        fraction 1                 Back-half                  "Hg, only"
Metal                   probe and                  fraction 2                 impingers
                        filter                     impingers 1-3                4-6



                                       *                          *                                               *
Antimony                7.7 (0.7)                  3.8 (0.4)                                   11.5 (1.1)
                                           *                      *                                               *
Arsenic                 12.7 (0.3)                 6.4 (0.1)                                   19.1 (0.4)

Barium                  0.5                        0.3                                         0.8
                                               *                          *                                           *
Beryllium               0.07 (0.05)                0.04 (0.03)                                 0.11 (0.08)
                                           *                          *                                           *
Cadmium                 1.0 (0.02)                 0.5 (0.01)                                  1.5 (0.03)
                                       *                          *                                           *
Chromium                1.7 (0.2)                  0.8 (0.1)                                   2.5 (0.3)

Copper                  1.4                        0.7                                         2.1
                                           *                      *                                               *
Lead                    10.1 (0.2)                 5.0 (0.1)                                   15.1 (0.3)
                                       *                          *                                       *
Manganese               0.5 (0.2)                  0.2 (0.1)                                   0.7 (0.3 )
                              **                         **                         **               **
Mercury                 0.6                        3.0                        2.0              5.6

Nickel                  3.6                        1.8                                         5.4

Phosphorus              18                         9                                           27
                                   *                          *                                           *
Selenium                18 (0.5)                   9 (0.3)                                     27 (0.8)
 Silver                 1.7                    0.9                                            2.6
                                    *                      *                                               *
 Thallium               9.6 (0.2)              4.8 (0.1)                                      14.4 (0.3)

 Zinc                   0.5                    0.3                                            0.8



     *
( ) Detection limit when analyzed by GFAAS.
**
 Detection limit when analyzed by CVAAS, estimated for Back Half and Total Train.
Note: Actual method in-stack detection limits will be determined based on actual source sampling parameters and
analytical results as described earlier in this section.

         ! Conversely, reducing stack gas sample volume and increasing sample liquid volume will
increase in-stack detection limits (the method would then be less sensitive). The front-half and back-half
samples (Fractions 1A plus and 2A) can be combined proportionally (see section 3.1.1.2 of this
methodology) prior to analysis. The resultant liquid volume (excluding the mercury fractions, which must
be analyzed separately) is recorded. Combining the sample as described does not allow determination
(whether front or back half) of where in the train the sample was captured. The in-stack method detection
limit then becomes a single value for all metals except mercury, for which the contribution of the mercury
fractions must be considered.

       ! The above discussion assumes no blank correction. Blank corrections are discussed later in this
method.

       3.1.2.3 Precision. The precisions (relative standard deviation) for each metal detected in a
method development test at a sewage sludge incinerator, are as follows: Sb (12.7%), As (13.5%), Ba
(20.6%), Cd (11.5%), Cr (11.2%), Cu (11.5%), Pb (11.6%), P (14.6%), Se (15.3%), T1 (12.3%), and Zn
(11.8%). The precision for nickel was 7.7% for another test conducted at a source simulator. Beryllium,
manganese, and silver were not detected in the tests; however, based on the analytical sensitivity of the
ICAP for these metals, it is assumed that their precisions should be similar to those for the other metals,
when detected at similar levels.

        3.1.2.4 Interferences. Iron can be a spectral interference during the analysis of arsenic,
chromium, and cadmium by ICAP. Aluminum can be a spectral interference during the analysis of arsenic
and lead by ICAP. Generally, these interferences can be reduced by diluting the sample, but this
increases the method detection limit (in-stack detection limit). Refer to EPA method 6010 (SW-846) or the
other analytical methods used for details on potential interferences for this method. The analyst must
eliminate or reduce interferences to acceptable levels. For all GFAAS analyses, matrix modifiers should
be used to limit interferences, and standards should be matrix matched.

3.1.3 Apparatus

        3.1.3.1 Sampling Train. A schematic of the sampling train is shown in Figure 3.1-1. It is similar to
the 40 CFR part 60, appendix A method 5 train. The sampling train consists of the following components:

         3.1.3.1.1 Probe Nozzle (Probe Tip) and Borosilicate or Quartz Glass Probe Liner. Same as
method 5, sections 2.1.1 and 2.1.2, except that glass nozzles are required unless an alternate probe tip
prevents the possibility of contamination or interference of the sample with its materials of construction. If
a probe tip other than glass is used, no correction (because of any effect on the sample by the probe tip)
of the stack sample test results can be made.

        3.1.3.1.2 Pitot Tube and Differential Pressure Gauge. Same as method 2, sections 2.1 and 2.2,
respectively.
         3.1.3.1.3 Filter Holder. Glass, same as method 5, section 2.1.5, except that a Teflon filter support
or other non-metallic, non-contaminating support must be used to replace the glass frit.

        3.1.3.1.4 Filter Heating System. Same as method 5, section 2.1.6.

         3.1.3.1.5 Condenser. The following system shall be used for the condensation and collection of
gaseous metals and for determining the moisture content of the stack gas. The condensing system
should consist of four to seven impingers connected in series with leak-free ground glass fittings or other
leak-free, non-contaminating fittings. The first impinger is optional and is recommended as a moisture
knockout trap for use during test conditions which require such a trap. The first impinger shall be
appropriately-sized, if necessary, for an expected large moisture catch and generally constructed as
described for the first impinger in method 5, paragraph 2.1.7. The second impinger (or the first
HNO3/H2O2 impinger) shall also be constructed as described for the first impinger in method 5. The third
impinger (or the second HNO3/H2O2 impinger) shall be the same as the Greenburg Smith impinger with
the standard tip described as the second impinger in method 5, paragraph 2.1.7. All other impingers used
in the methods train are the same as the first HNO3/H2O2 impinger described in this paragraph. In
summary, the first impinger which may be optional as described in this methodology shall be empty, the
second and third shall contain known quantities of a nitric acid/hydrogen peroxide solution (section
3.l.4.2.1), the fourth shall be empty, the fifth and sixth shall contain a known quantity of acidic potassium
permanganate solution (section 3.1.4.2.2), and the last impinger shall contain a known quantity of silica
gel. A thermometer capable of measuring to within 1C (2F) shall be placed at the outlet of the last
impinger. When the moisture knockout impinger is not needed, it is removed from the train and the other
impingers remain the same. If mercury analysis is not to be performed, the potassium permanganate
impingers and the empty impinger preceding them are removed.

>>>> See the accompanying hardcopy volume for non-machine-readable data that appears at this point.
<<<<

       3.1.3.1.6 Metering System, Barometer, and Gas Density Determination Equipment. Same as
method 5, sections 2.1.8 through 2.1.10, respectively.

       3.1.3.1.7 Teflon Tape. For capping openings and sealing connections, if necessary, on the
sampling train.

        3.1.3.2 Sample Recovery. Same as method 5, sections 2.2.1 through 2.2.8 (Nonmetallic
Probe-Liner and Probe-Nozzle Brushes or Swabs, Wash Bottles, Sample Storage Containers, Petri
Dishes, Glass Graduated Cylinder, Plastic Storage Containers, Funnel and Rubber Policeman, and Glass
Funnel), respectively, with the following exceptions and additions:

        3.1.3.2.1 Nonmetallic Probe-Liner and Probe-Nozzle Brushes or Swabs. For quantitative recovery
of materials collected in the front half of the sampling train: Description of acceptable all-Teflon
component brushes or swabs is to be included in EPA's Emission Measurement Technical Information
Center (EMTIC) files.

         3.1.3.2.2 Sample Storage Containers. Glass bottles with Teflon-lined caps which are non-reactive
to the oxidizing solutions, with a capacity of 1000- and 500-ml, shall be used for KMnO4-containing
samples and blanks. Polyethylene bottles may be used for other sample types.

        3.1.3.2.3 Graduated Cylinder. Glass or equivalent.

        3.1.3.2.4 Funnel. Glass or equivalent.

        3.1.3.2.5 Labels. For identification of samples.

       3.1.3.2.6 Polypropylene Tweezers and/or Plastic Gloves. For recovery of the filter from the
sampling train filter holder.
        3.1.3.3 Sample Preparation and Analysis. For the analysis, the following equipment is needed:

       3.1.3.3.1 Volumetric Flasks, 100-ml, 250-ml, and 1000-ml. For preparation of standards and
sample dilution.

        3.1.3.3.2 Graduated Cylinders. For preparation of reagents.
                      R
        3.1.3.3.3 Parr Bombs or Microwave Pressure Relief Vessels with Capping Station (GEM
Corporation model or equivalent).
        3.1.3.3.4 Beakers and Watchglasses. 250-ml beakers for sample digestion with watchglasses to
cover the tops.

        3.1.3.3.5 Ring Stands and Clamps. For securing equipment such as filtration apparatus.

        3.1.3.3.6 Filter Funnels. For holding filter paper.

        3.1.3.3.7 Whatman 541 Filter Paper (or equivalent). For filtration of digested samples.

        3.1.3.3.8 Disposable Pasteur Pipets and Bulbs.

        3.1.3.3.9 Volumetric Pipets.

        3.1.3.3.10 Analytical Balance. Accurate to within 0.1 mg.

       3.1.3.3.11 Microwave or Conventional Oven. For heating samples at fixed power levels or
temperatures.

        3.1.3.3.12 Hot Plates.

        3.1.3.3.13 Atomic Absorption Spectrometer (AAS). Equipped with a background corrector.

         3.1.3.3.13.1 Graphite Furnace Attachment. With antimony, arsenic, cadmium, lead, selenium,
thallium hollow cathode lamps (HCLs) or electrodeless discharge lamps (EDLs). (Same as EPA SW-846
methods 7041 (antimony), 7060 (arsenic), 7131 (cadmium), 7421 (lead), 7740 (selenium), and 7841
(thallium).)

       3.1.3.3.13.2 Cold Vapor Mercury Attachment. With a mercury HCL or EDL. The equipment
needed for the cold vapor mercury attachment includes an air recirculation pump, a quartz cell, an aerator
apparatus, and a heat lamp or desiccator tube. The heat lamp should be capable of raising the ambient
temperature at the quartz cell by 10C such that no condensation forms on the wall of the quartz cell.
(Same as EPA method 7470.)

        3.1.3.3.14 Inductively Coupled Argon Plasma Spectrometer. With either a direct or sequential
reader and an alumina torch. (Same as EPA method 6010.)

3.1.4 Reagents

         The complexity of this methodology is such that to obtain reliable results, the testers (Including
analysts) should be experienced and knowledgeable in source sampling, in handling and preparing
(including mixing) reagents as described, and using adequate safety procedures and protective
equipment in performing this method, including sampling, mixing reagents, digestions, and analyses.
Unless otherwise indicated, it is intended that all reagents conform to the specifications established by the
Committee on Analytical Reagents of the American Chemical Society, where such specifications are
available; otherwise, use the best available grade.
        3.1.4.1 Sampling. The reagents used in sampling are as follows:
                                                                      2
         3.1.4.1.1 Filters. The filters shall contain less than 1.3 g/in of each of the metals to be
measured. Analytical results provided by filter manufacturers are acceptable. However, if no such results
are available, filter blanks must be analyzed for each target metal prior to emission testing. Quartz fiber or
                                                                            2
glass fiber (which meet the requirement of containing less than 1.3 g/in of each metal) filters without
organic binders shall be used. The filters should exhibit at least 99.95 percent efficiency (<0.05 percent
penetration) on 0.3 micron dioctyl phthalate smoke particles. The filter efficiency test shall be conducted
in accordance with ASTM Standard Method D2986-7l (incorporated by reference). For particulate
determination in sources containing SO2 or SO3, the filter material must be of a type that is unreactive to
SO2 or SO3, as described in EPA method 5. Quartz fiber filters meeting these requirements are
recommended for use in this method.

        3.1.4.1.2 Water. To conform to ASTM Specification Dl193.77, Type II (incorporated by reference).
If necessary, analyze the water for all target metals prior to field use. All target metal concentrations
should be less than 1 ng/ml.

        3.1.4.1.3 Nitric Acid. Concentrated. Baker Instra-analyzed or equivalent.

        3.1.4.1.4 Hydrochloric Acid. Concentrated. Baker Instra-analyzed or equivalent.

        3.1.4.1.5 Hydrogen Peroxide, 30 Percent (V/V).

        3.1.4.1.6 Potassium Permanganate.

        3.1.4.1.7 Sulfuric Acid. Concentrated.

        3.1.4.1.8 Silica Gel and Crushed Ice. Same as method 5, sections 3.1.2 and 3.1.4, respectively.

        3.1.4.2 Pretest Preparation for Sampling Reagents.

         3.1.4.2.1 Nitric Acid (HNO3)/Hydrogen Peroxide (H2O2) Absorbing Solution, 5 Percent HNO3/10
Percent H2O2. Carefully with stirring, add 50 ml of concentrated HNO 3 to a 1000-ml volumetric flask
containing approximately 500 ml of water, and then, carefully with stirring, add 333 ml of 30 percent H 2O2.
Dilute to volume (1000 ml) with water. Mix well. The reagent shall contain less than 2 ng/ml of each target
metal.

         3.1.4.2.2 Acidic Potassium Permanganate (KMnO4) Absorbing Solution, 4 Percent KMnO4 (W/V),
10 Percent H2SO4 (V/V). Prepare fresh daily. Mix carefully, with stirring, 100 ml of concentrated H 2SO4
into 800 ml of water, and add water with stirring to make a volume of 1 L: This solution is 10 percent
H2SO4 (V/V). Dissolve, with stirring, 40 g of KMnO4 into 10 percent H2SO4 (V/V) and add 10 percent
H2SO4 (V/V) with stirring to make a volume of 1 L: this is the acidic potassium permanganate absorbing
solution. Prepare and store in glass bottles to prevent degradation. The reagent shall contain less than 2
ng/ml of Hg.

         Precaution: To prevent autocatalytic decomposition of the permanganate solution, filter the
solution through Whatman 541 filter paper. Also, due to the potential reaction of the potassium
permanganate with the acid, there may be pressure buildup in the sample storage bottle; these bottles
shall not be fully filled and shall be vented both to relieve potential excess pressure and prevent explosion
due to pressure buildup. Venting is required, but should not allow contamination of the sample; a No.
70-72 hole drilled in the container cap and Teflon liner has been used.

        3.1.4.2.3 Nitric Acid, 0.1 N. With stirring, add 6.3 ml of concentrated HNO3 (70 percent) to a flask
containing approximately 900 ml of water. Dilute to 1000 ml with water. Mix well. The reagent shall
contain less than 2 ng/ml of each target metal.
         3.1.4.2.4 Hydrochloric Acid (HCl), 8 N. Make the desired volume of 8 N HCl in the following
proportions. Carefully with stirring, add 690 ml of concentrated HCl to a flask containing 250 ml of water.
Dilute to 1000 ml with water. Mix well. The reagent shall contain less than 2 ng/ml of Hg.

        3.1.4.3 Glassware Cleaning Reagents.

        3.1.4.3.1 Nitric Acid, Concentrated. Fisher ACS grade or equivalent.

        3.1.4.3.2 Water. To conform to ASTM Specifications D1193-77, Type II.

        3.1.4.3.3 Nitric Acid, 10 Percent (V/V). With stirring, add 500 ml of concentrated HNO3 to a flask
containing approximately 4000 ml of water. Dilute to 5000 ml with water. Mix well. Reagent shall contain
less than 2 ng/ml of each target metal.

        3.1.4.4 Sample Digestion and Analysis Reagents.

        3.1.4.4.1 Hydrochloric Acid, Concentrated.

        3.1.4.4.2 Hydrofluoric Acid, Concentrated.

        3.1.4.4.3 Nitric Acid, Concentrated. Baker Instra-analyzed or equivalent.

        3.1.4.4.4 Nitric Acid, 50 Percent (V/V). With stirring, add 125 ml of concentrated HNO 3 to 100 ml
of water. Dilute to 250 ml with water. Mix well. Reagent shall contain less than 2 ng/ml of each target
metal.

        3.1.4.4.5 Nitric Acid, 5 Percent (V/V). With stirring, add 50 ml of concentrated HNO 3 to 800 ml of
water. Dilute to 1000 ml with water. Mix well. Reagent shall contain less than 2 ng/ml of each target
metal.

        3.1.4.4.6 Water. To conform to ASTM Specifications D1193-77, Type II.

        3.1.4.4.7 Hydroxylamine Hydrochloride and Sodium Chloride Solution. See EPA method 7470 for
preparation.

        3.1.4.4.8 Stannous Chloride. See method 7470.

        3.1.4.4.9 Potassium Permanganate, 5 Percent (W/V). See method 7470.

        3.1.4.4.10 Sulfuric Acid, Concentrated.

        3.1.4.4.11 Nitric Acid, 50 Percent (V/V).

        3.1.4.4.12 Potassium Persulfate, 5 Percent (W/V). See Method 7470.

        3.1.4.4.13 Nickel Nitrate, Ni(NO3)2. 6H2O.

        3.1.4.4.14 Lanthanum, Oxide, La2O3.

        3.1.4.4.15 AAS Grade Hg Standard, 1000 g/ml.

        3.1.4.4.16 AAS Grade Pb Standard, 1000 g/ml.

        3.1.4.4.17 AAS Grade As Standard, 1000 g/ml.

        3.1.4.4.18 AAS Grade Cd Standard, 1000 g/ml.
        3.1.4.4.19 AAS Grade Cr Standard, 1000 g/ml.

        3.1.4.4.20 AAS Grade Sb Standard, 1000 g/ml.

        3.1.4.4.21 AAS Grade Ba Standard, 1000 g/ml.

        3.1.4.4.22 AAS Grade Be Standard, 1000 g/ml.

        3.1.4.4.23 AAS Grade C Standard, 1000 g/ml.

        3.1.4.4.24 AAS Grade Mn Standard, 1000 g/ml.

        3.1.4.4.25 AAS Grade Ni Standard, 1000 g/ml.

        3.1.4.4.26 AAS Grade P Standard, 1000 g/ml.

        3.1.4.4.27 AAS Grade Se Standard, 1000 g/ml.

        3.1.4.4.28 AAS Grade Ag Standard, 1000 g/ml.

        3.1.4.4.29 AAS Grade T1 Standard, 1000 g/ml.

        3.1.4.4.30 AAS Grade Zn Standard, 1000 g/ml.

        3.1.4.4.31 AAS Grade Al Standard, 1000 g/ml.

        3.1.4.4.32 AAS Grade Fe Standard, 1000 g/ml.

        3.1.4.4.33 The metals standards may also be made from solid chemicals as described in EPA
Method 200.7. EPA SW-846 Method 7470 or Standard Methods for the Analysis of Water and
Wastewater, 15th Edition, Method 303F should be referred to for additional information on mercury
standards.

         3.1.4.4.34 Mercury Standards and Quality Control Samples. Prepare fresh weekly a 10 g/ml
intermediate mercury standard by adding 5 ml of 1000 g/ml mercury stock solution to a 500-ml
volumetric flask; dilute with stirring to 500 ml by first carefully adding 20 ml of 15 percent HNO 3 and then
adding water to the 500-ml volume. Mix well. Prepare a 200 ng/ml working mercury standard solution
fresh daily: Add 5 ml of the 10 g/ml intermediate standard to a 250-ml volumetric flask and dilute to 250
ml with 5 ml of 4 percent KMnO4, 5 ml of 15 percent HNO3, and then water. Mix well. At least six separate
aliquots of the working mercury standard solution should be used to prepare the standard curve. These
aliquots should contain 0.0, 1.0, 2.0, 3.0, 4.0, and 5.0 ml of the working standard solution containing 0,
200, 400, 600, 800, and 1000 ng mercury, respectively. Quality control samples should be prepared by
making a separate 10 g/ml standard and diluting until in the range of the calibration.

        3.1.4.4.35 ICAP Standards and Quality Control Samples. Calibration standards for ICAP analysis
can be combined into four different mixed standard solutions as shown below.

Mixed Standard Solutions for ICAP Analysis



Solution                                                Elements



I                                                       As, Be, Cd, Mn, Pb, Se, Zn.
II                                                       Ba, Cu, Fe.
III                                                      Al, Cr, Ni.
IV                                                       Ag, P, Sb, Tl.



         Prepare these standards by combining and diluting the appropriate volumes of the 1000 g/ml
solutions with 5 percent nitric acid. A minimum of one standard and a blank can be used to form each
calibration curve. However, a separate quality control sample spiked with known amounts of the target
metals in quantities in the midrange of the calibration curve should be prepared. Suggested standard
levels are 25 g/ml for Al, Cr, and Pb, 15 g/ml for Fe, and 10 g/ml for the remaining elements.
Standards containing less than 1 g/ml of metal should be prepared daily. Standards containing greater
than 1 g/ml of metal should be stable for a minimum of 1 to 2 weeks.

         3.1.4.4.36 Graphite Furnace AAS Standards. Antimony, arsenic, cadmium, lead, selenium, and
thallium. Prepare a 10 g/ml standard by adding 1 ml of 1000 g/ml standard to a 100-ml volumetric
flask. Dilute with stirring to 100 ml with 10 percent nitric acid. For graphite furnace AAS, the standards
must be matrix matched. Prepare a 100 ng/ml standard by adding 1 ml of the 10 g/ml standard to a
110-ml volumetric flask and dilute to 100 ml with the appropriate matrix solution. Other standards should
be prepared by dilution of the 100 ng/ml standards. At least five standards should be used to make up the
standard curve. Suggested levels are 0, 10, 50, 75, and 100 ng/ml. Quality control samples should be
prepared by making a separate 10 g/ml standard and diluting until it is in the range of the samples.
Standards containing less than 1 g/ml of metal should be prepared daily. Standards containing greater
than 1 g/ml of metal should be stable for a minimum of 1 to 2 weeks.

        3.1.4.4.3 Matrix Modifiers.

        3.1.4.4.37.1 Nickel Nitrate, 1 Percent (V/V). Dissolve 4.956 g of Ni(NO 3)2. 6H2O in approximately
50 ml of water in a 100-ml volumetric flask. Dilute to 100 ml with water.

        3.1.4.4.37.2 Nickel Nitrate, 0.1 Percent (V/V). Dilute 10 ml of the 1 percent nickel nitrate solution
from section 4.4.37.1 above to 100 ml with water. Inject an equal amount of sample and this modifier into
the graphite furnace during AAS analysis for As.

         3.1.4.4.37.3 Lanthanum. Carefully dissolve 0.5864 g of La2O3 in 10 ml of concentrated HNO3 and
dilute the solution by adding it with stirring to approximately 50 ml of water, and then dilute to 100 ml with
water. Mix well. Inject an equal amount of sample and this modifier into the graphite furnace during AAS
analysis for Pb.

3.1.5 Procedure

        3.1.5.1 Sampling. The complexity of this method is such that, to obtain reliable results, testers
and analysts should be trained and experienced with the test procedures, including source sampling,
reagent preparation and handling, sample handling, analytical calculations, reporting, and descriptions
specifically at the beginning of and throughout section 3.1.4 and all other sections of this methodology.

         3.1.5.1.1 Pretest Preparation. Follow the same general procedure given in method 5, section
4.1.1, except that, unless particulate emissions are to be determined, the filter need not be desiccated or
weighed. All sampling train glassware should first be rinsed with hot tap water and then washed in hot
soapy water. Next, glassware should be rinsed three times with tap water, followed by three additional
rinses with water. All glassware should then be soaked in a 10 percent (V/V) nitric acid solution for a
minimum of 4 hours, rinsed three times with water, rinsed a final time with acetone, and allowed to air dry.
All glassware openings where contamination can occur should be covered until the sampling train is
assembled for sampling.

        3.1.5.1.2 Preliminary Determinations. Same as method 5, section 4.1.2.
          3.1.5.1.3 Preparation of Sampling Train. Follow the same general procedures given in method 5,
section 4.1.3, except place 100 ml of the nitric acid/hydrogen peroxide solution (section 3.1.4.2.1) in each
of the two HNO3/H2O2 impingers as shown in Figure 3.1-1 (normally the second and third impingers),
place 100 ml of the acidic potassium permanganate absorbing solution (section 3.1.4.2.2) in each of the
two permanganate impingers as shown in Figure A-1, and transfer approximately 200 to 300 g of
preweighed silica gel from its container to the last impinger. Alternatively, the silica gel may be weighed
directly in the impinger just prior to train assembly.

         Several options are available to the tester based on the sampling requirements and conditions.
The use of an empty first impinger can be eliminated if the moisture to be collected in the impingers will
be less than approximately 100 ml. If necessary, use as applicable to this methodology the procedure
described in section 7.1.1 of EPA method 101A, 40 CFR part 61, appendix B, to maintain the desired
color in the last permanganate impinger.
         Retain for reagent blanks volumes of the nitric acid/hydrogen peroxide solution per section
3.1.5.2.9 of this method and of the acidic potassium permanganate solution per section 3.1.5.2.10. These
reagent blanks should be labeled and analyzed as described in section 3.1.7. Set up the sampling train
as shown in Figure 3.1-1, or if mercury analysis is not to be performed in the train, then it should be
modified by removing the two permanganate impingers and the impinger preceding the permanganate
impingers. If necessary to ensure leak-free sampling train connections and prevent contamination Teflon
tape or other non-contaminating material should be used instead of silicone grease.

        Precaution: Extreme care should be taken to prevent contamination within the train. Prevent the
mercury collection reagent (acidic potassium permanganate) from contacting any glassware of the train
which is washed and analyzed for Mn. Prevent hydrogen peroxide from mixing with the acidic potassium
permanganate.

         Mercury emissions can be measured, alternatively, in a separate train which measures only
mercury emissions by using EPA method 101A with the modifications described below (and with the
further modification that the permanganate containers shall be processed as described in the precaution
in section 3.1.4.2.2 and the note in section 3.1.5.2.5 of this methodology). This alternative method is
applicable for measurement of mercury emissions, and it may be of special interest to sources which
must measure both mercury and manganese emissions.

        Section 7.2.1 of method 101A shall be modified as follows after the 250 to 400-ml KMnO4 rinse:

          To remove any precipitated material and any residual brown deposits on the glassware following
the permanganate rinse, rinse with approximately 100 ml of deionized distilled water, and add this water
rinse carefully assuring transfer of all loose precipitated materials from the three permanganate impingers
into the permanganate Container No. 1. If no visible deposits remain after this water rinse, do not rinse
with 8 N HCl. However, if deposits do remain on the glassware after this water rinse, wash the impinger
surfaces with 25 ml of 8 N HCl, and place the wash in a separate sample container labeled Container No.
1.A. containing 200 ml of water as follows. Place 200 ml of water in a sample container labeled Container
No. 1.A. Wash the impinger walls and stem with the HCl by turning the impinger on its side and rotating it
so that the HCl contacts all inside surfaces. Use a total of only 25 ml of 8 N HCl for rinsing all
permanganate impingers combined. Rinse the first impinger, then pour the actual rinse used for the first
impinger into the second impinger for its rinse, etc. Finally, pour the 25 ml of 8 N HCl rinse carefully with
stirring into Container No. 1.A. Analyze the HCl rinse separately by carefully diluting with stirring the
contents of Container No. 1.A. to 500 ml with deionized distilled water. Filter (if necessary) through
Whatman 40 filter paper, and then analyze for mercury according to section 7.4, except limit the aliquot
size to a maximum of 10 ml. Prepare and analyze a water diluted blank 8 N HCl sample by using the
same procedure as that used by Container No. 1.A., except add 5 ml of 8 N HCl with stirring to 40 ml of
water, and then dilute to 100 ml with water. Then analyze as instructed for the sample from Container No.
1.A. Because the previous separate permanganate solution rinse (section 7.2.1) and water rinse (as
modified in these guidelines) have the capability to recover a very high percentage of the mercury from
the permanganate impingers, the amount of mercury in the HCl rinse in Container No. 1.A. may be very
small, possibly even insignificantly small. However, add the total of any mercury analyzed and calculated
for the HCl rinse sample Container No. 1.A. to that calculated from the mercury sample from section 7.3.2
which contains the separate permanganate rinse (and water rinse as modified herein) for calculation of
the total sample mercury concentration.

         3.1.5.1.4 Leak-Check Procedures. Follow the leak-check procedures given in method 5, section
4.1.4.1 (Pretest Leak-Check), section 4.1.4.2 (Leak-Checks During the Sample Run), and section 4.1.4.3
(Post-Test Leak-Checks).
         3.1.5.1.5 Sampling Train Operation. Follow the procedures given in method 5, section 4.1.5. For
each run, record the data required on a data sheet such as the one shown in Figure 5-2 of method 5.

        3.1.5.1.6 Calculation of Percent Isokinetic. Same as method 5, section 4.1.6.

         3.1.5.2 Sample Recovery. Begin cleanup procedures as soon as the probe is removed from the
stack at the end of a sampling period.

         The probe should be allowed to cool prior to sample recovery. When it can be safely handled,
wipe off all external particulate matter near the tip of the probe nozzle and place a rinsed,
non-contaminating cap over the probe nozzle to prevent losing or gaining particulate matter. Do not cap
the probe tip tightly while the sampling train is cooling. This normally causes a vacuum to form in the filter
holder, thus causing the undesired result of drawing liquid from the impingers into the filter.

        Before moving the sampling train to the cleanup site, remove the probe from the sampling train
and cap the open outlet. Be careful not to lose any condensate that might be present. Cap the filter inlet
where the probe was fastened. Remove the umbilical cord from the last impinger and cap the impinger.
Cap off the filter holder outlet and impinger inlet. Use noncontaminating caps, whether ground-glass
stoppers, plastic caps, serum caps, or Teflon tape to close these openings.

        Alternatively, the train can be disassembled before the probe and filter holder/oven are
completely cooled, if this procedure is followed: Initially disconnect the filter holder outlet/impinger inlet
and loosely cap the open ends. Then disconnect the probe from the filter holder or cyclone inlet and
loosely cap the open ends. Cap the probe tip and remove the umbilical cord as previously described.

        Transfer the probe and filter-impinger assembly to a cleanup area that is clean and protected
from the wind and other potential causes of contamination or loss of sample. Inspect the train before and
during disassembly and note any abnormal conditions. The sample is recovered and treated as follows
(see schematic in Figure 3.1-2). Ensure that all items necessary for recovery of the sample do not
contaminate it.

          3.1.5.2.1 Container No. 1 (Filter). Carefully remove the filter from the filter holder and place it in its
identified petri dish container. Acid-washed polypropylene or Teflon coated tweezers or clean, disposable
surgical gloves rinsed with water and dried should be used to handle the filters. If it is necessary to fold
the filter, make certain the particulate cake is inside the fold. Carefully transfer the filter and any
particulate matter or filter fibers that adhere to the filter holder gasket to the petri dish by using a dry
(acid-cleaned) nylon bristle brush. Do not use any metalcontaining materials when recovering this train.
Seal the labeled petri dish.

>>>> See the accompanying hardcopy volume for non-machine-readable data that appears at this point.
<<<<

        3.1.5.2.2 Container No. 2 (Acetone Rinse).

         Note: Perform section 3.1.5.2.2 only if determination of particulate emissions are desired in
addition to metals emissions. If only metals emissions are desired, skip section 3.1.5.2.2 and go to
section 3.1.5.2.3. Taking care to see that dust on the outside of the probe or other exterior surfaces does
not get into the sample, quantitatively recover particulate matter and any condensate from the probe
nozzle, probe fitting (plastic such as Teflon, polypropylene, etc. fittings are recommended to prevent
contamination by metal fittings; further, if desired, a single glass piece consisting of a combined probe tip
and probe liner may be used, but such a single glass piece is not a requirement of this methodology),
probe liner, and front half of the filter holder by washing these components with 100 ml of acetone and
placing the wash in a glass container.

         Note: The use of exactly 100 ml is necessary for the subsequent blank correction procedures.
Distilled water may be used instead of acetone when approved by the Administrator and shall be used
when specified by the Administrator; in these cases, save a water blank and follow the Administrator's
directions on analysis. Perform the acetone rinses as follows: Carefully remove the probe nozzle and
clean the inside surface by rinsing with acetone from a wash bottle and brushing with a nonmetallic brush.
Brush until the acetone rinse shows no visible particles, after which make a final rinse of the inside
surface with acetone.

         Brush and rinse the sample-exposed, inside parts of the fitting with acetone in a similar way until
no visible particles remain.

         Rinse the probe liner with acetone by tilting and rotating the probe while squirting acetone into its
upper end so that all inside surfaces will be wetted with acetone. Allow the acetone to drain from the
lower end into the sample container. A funnel may be used to aid in transferring liquid washings to the
container. Follow the acetone rinse with a nonmetallic probe brush. Hold the probe in an inclined position,
squirt acetone into the upper end as the probe brush is being pushed with a twisting action through the
probe; hold a sample container underneath the lower end of the probe, and catch any acetone and
particulate matter which is brushed through the probe three times or more until none remains in the probe
liner on visual inspection. Rinse the brush with acetone, and quantitatively collect these washings in the
sample container. After the brushing, make a final acetone rinse of the probe as described above.

        It is recommended that two people clean the probe to minimize sample losses. Between sampling
runs, keep brushes clean and protected from contamination.

         Clean the inside of the front half of the filter holder by rubbing the surfaces with a nonmetallic
nylon bristle brush and rinsing with acetone. Rinse each surface three times or more if needed to remove
visible particulate. Make a final rinse of the brush and filter holder. After all acetone washings and
particulate matter have been collected in the sample container tighten the lid on the sample container so
that acetone will not leak out when it is shipped to the laboratory. Mark the height of the fluid level to
determine whether or not leakage occurred during transport. Label the container clearly to identify its
contents.

         3.1.5.2.3 Container No. 3 (Probe Rinse). Keep the probe assembly clean and free from
contamination as described in section 3.1.5.2.2 of this method during the 0.1 N nitric acid rinse described
below. Rinse the probe nozzle and fitting probe liner, and front half of the filter holder thoroughly with 100
ml of 0.1 N nitric acid and place the wash into a sample storage container.

        Note: The use of exactly 100 ml is necessary for the subsequent blank correction procedures.
Perform the rinses as applicable and generally as described in method 12, section 5.2.2. Record the
volume of the combined rinse. Mark the height of the fluid level on the outside of the storage container
and use this mark to determine if leakage occurs during transport. Seal the container and clearly label the
contents. Finally, rinse the nozzle, probe liner, and front half of the filter holder with water followed by
acetone and discard these rinses.

         3.1.5.2.4 Container No. 4 (Impingers 1 through 3, HNO 3/H2O2 Impingers and Moisture Knockout
Impinger, when used, Contents and Rinses). Due to the potentially large quantity of liquid involved, the
tester may place the impinger solutions from impingers 1 through 3 in more than one container. Measure
the liquid in the first three impingers volumetrically to within 0.5 ml using a graduated cylinder. Record the
volume of liquid present. This information is required to calculate the moisture content of the sampled flue
gas. Clean each of the first three impingers, the filter support, the back half of the filter housing, and
connecting glassware by thoroughly rinsing with 100 ml of 0.1 N nitric acid using the procedure as
applicable and generally as described in method 12, section 5.2.4.

         Note: The use of exactly 100 ml of 0.1 N nitric acid rinse is necessary for the subsequent blank
correction procedures. Combine the rinses and impinger solutions, measure and record the volume. Mark
the height of the fluid level on the outside of the container to determine if leakage occurs during transport.
Seal the container and clearly label the contents.

         3.1.5.2.5 Container Nos. 5A, 5B, and 5C. 5A (0.1 N HNO 3), 5B (KMnO4/H2SO4 absorbing
solution), and 5C (8 N HCl rinse and dilution). (As described previously at the end of section 3.1.3.1.5 of
this method, if mercury is not being measured in this train, then impingers 4, 5, and 6, as shown in Figure
3.1-2, are not necessary and may be eliminated.) Pour all the liquid, if any, from the impinger which was
empty at the start of the run and which immediately precedes the two permanganate impingers (normally
impinger No. 4) into a graduated cylinder and measure the volume to within 0.5 ml. This information is
required to calculate the moisture content of the sampled flue gas. Place the liquid in Sample Container
No. 5A. Rinse the impinger (No. 4) with 100 ml of 0.1 N HNO3 and place this into Container No. 5A.

          Pour all the liquid from the two permanganate impingers into a graduated cylinder and measure
the volume to within 0.5 ml. This information is required to calculate the moisture content of the sampled
flue gas. Place this KMnO4 absorbing solution stack sample from the two permanganate impingers into
Container No. 5B. Using 100 ml total of fresh acidified potassium permanganate solution, rinse the two
permanganate impingers and connecting glass pieces a minimum of three times and place the rinses into
Container No. 5B, carefully ensuring transfer of all loose precipitated materials from the two impingers
into Container No. 5B. Using 100 ml total of water, rinse the permanganate impingers and connecting
glass pieces a minimum of three times, and place the rinses into Container 5B, carefully ensuring transfer
of all loose precipitated material, if any, from the two impingers into Container No. 5B. Mark the height of
the fluid level on the outside of the bottle to determine if leakage occurs during transport. See the
following note and the precaution in paragraph 3.1.4.2.2 and properly prepare the bottle and clearly label
the contents.

        Note: Due to the potential reaction of the potassium permanganate with the acid, there may be
pressure buildup in the sample storage bottles. These bottles shall not be completely filled and shall be
vented to relieve potential excess pressure. Venting is required. A No. 70-72 hole drilled in the container
cap and Teflon liner has been used.

         If no visible deposits remain after the above described water rinse, do not rinse with 8 N HCl.
However, if deposits do remain on the glassware after this water rinse, wash the impinger surfaces with
25 ml of 8 N HCl, and place the wash in a separate sample container labeled Container No. 5C
containing 200 ml of water as follows: Place 200 ml of water in a sample container labeled Container No.
5C. Wash the impinger walls and stem with the HCl by turning the impinger on its side and rotating it so
that the HCl contacts all inside surfaces. Use a total of only 25 ml of 8 N HCl for rinsing both permananate
impingers combined. Rinse the first impinger, then pour the actual rinse used for the first impinger into the
second impinger for its rinse. Finally, pour the 25 ml of 8 N HCl rinse carefully with stirring into Container
No. 5C. Mark the height of the fluid level on the outside of the bottle to determine if leakage occurs during
transport.

       3.1.5.2.6 Container No. 6 (Silica Gel). Note the color of the indicating silica gel to determine
whether it has been completely spent and make a notation of its condition. Transfer the silica gel from its
impinger to its original container and seal. The tester may use a funnel to pour the silica gel and a rubber
policeman to remove the silica gel from the impinger.

         The small amount of particles that may adhere to the impinger wall need not be removed. Do not
use water or other liquids to transfer the silica gel since weight gained in the silica gel impinger is used for
moisture calculations. Alternatively, if a balance is available in the field, record the weight of the spent
silica gel (or silica gel plus impinger) to the nearest 0.5 g.
         3.1.5.2.7 Container No. 7 (Acetone Blank). If particulate emissions are to be determined, at least
once during each field test, place a 100-ml portion of the acetone used in the sample recovery process
into a labeled container for use in the front-half field reagent blank. Seal the container.

         3.1.5.2.8 Container No. 8A (0.1 N Nitric Acid Blank). At least once during each field test, place
300 ml of the 0.1 N nitric acid solution used in the sample recovery process into a labeled container for
use in the front-half and back-half field reagent blanks. Seal the container. Container No. 8B (water
blank). At least once during each field test, place 100 ml of the water used in the sample recovery
process into a labeled Container No. 8B. Seal the container.

        3.1.5.2.9 Container No. 9 (5% Nitric Acid/10% Hydrogen Peroxide Blank). At least once during
each field test, place 200 ml of the 5% nitric acid/10% hydrogen peroxide solution used as the nitric acid
impinger reagent into a labeled container for use in the back-half field reagent blank. Seal the container.

         3.1.5.2.10 Container No. 10 (Acidified Potassium Permanganate Blank). At least once during
each field test, place 100 ml of the acidified potassium permanganate solution used as the impinger
solution and in the sample recovery process into a labeled container for use in the back-half field reagent
blank for mercury analysis. Prepare the container as described in section 3.1.5.2.5.

        Note: Due to the potential reaction of the potassium permanganate with the acid, there may be
pressure buildup in the sample storage bottles. These bottles shall not be completely filled and shall be
vented to relieve potential excess pressure. Venting is required. A No. 70-72 hole drilled in the container
cap and Teflon liner has been used.

         3.1.5.2.11 Container No. 11 (8 N HCl Blank). At least once during each field test, perform both of
the following: Place 200 ml of water into a sample container. Pour 25 ml of 8N HCl carefully with stirring
into the 200 ml of water in the container. Mix well and seal the container.

           3.1.5.2.12 Container No. 12 (Filter Blank). Once during each field test, place three unused blank
filters from the same lot as the sampling filters in a labeled petri dish. Seal the petri dish. These will be
used in the front-half field reagent blank.

        3.1.5.3 Sample Preparation. Note the level of the liquid in each of the containers and determine if
any sample was lost during shipment. If a noticeable amount of leakage has occurred, either void the
sample or use methods, subject to the approval of the Administrator, to correct the final results. A
diagram illustrating sample preparation and analysis procedures for each of the sample train components
is shown in Figure 3.1-3.

          3.1.5.3.1 Container No. 1 (Filter). If particulate emissions are being determined, then desiccate
the filter and filter catch without added heat and weigh to a constant weight as described in section 4.3 of
method 5. For analysis of metals, divide the filter with its filter catch into portions containing approximately
0.5 g each and place into the analyst's choice of either individual microwave pressure relief vessels or
     ®
Parr Bombs. Add 6 ml of concentrated nitric acid and 4 ml of concentrated hydrofluoric acid to each
vessel. For microwave heating, microwave the sample vessels for approximately 12-15 minutes in
intervals of 1 to 2 minutes at 600 Watts. For conventional heating, heat the Parr Bombs at 140C
(285F) for 6 hours. Cool the samples to room temperature and combine with the acid digested probe
rinse as required in section 3.1.5.3.3, below.

>>>> See the accompanying hardcopy volume for non-machine-readable data that appears at this point.
<<<<

         Notes: 1. Suggested microwave heating times are approximate and are dependent upon the
number of samples being digested. Twelve to 15 minute heating times have been found to be acceptable
for simultaneous digestion of up to 12 individual samples. Sufficient heating is evidenced by sorbent
reflux within the vessel.
        2. If the sampling train uses an optional cyclone, the cyclone catch should be prepared and
digested using the same procedures described for the filters and combined with the digested filter
samples.

         3.1.5.3.2 Container No. 2 (Acetone Rinse). Note the level of liquid in the container and confirm on
the analysis sheet whether leakage occurred during transport. If a noticeable amount of leakage has
occurred, either void the sample or use methods, subject to the approval of the Administrator, to correct
the final results. Measure the liquid in this container either volumetrically to ± 1 ml or gravimetrically to ±
0.5 g. Transfer the contents to an acid-cleaned, tared 250-ml beaker and evaporate to dryness at ambient
temperature and pressure. If particulate emissions are being determined, desiccate for 24 hours without
added heat, weigh to a constant weight according to the procedures described in section 4.3 of method 5,
and report the results to the nearest 0.1 mg. Redissolve the residue with 10 ml of concentrated nitric acid
and, carefully with stirring, quantitatively combine the resultant sample including all liquid and any
particulate matter with Container No. 3 prior to beginning the following section 3.1.5.3.3.

          3.1.5.3.3 Container No. 3 (Probe Rinse). The pH of this sample shall be 2 or lower. If the pH is
higher, the sample should be acidified to pH 2 by the careful addition with stirring of concentrated nitric
acid. The sample should be rinsed into a beaker with water and the beaker should be covered with a
ribbed watchglass. The sample volume should be reduced to approximately 20 ml by heating on a hot
                                                                                             ®
plate at a temperature just below boiling. Digest the sample in microwave vessels or Parr Bombs by
quantitatively transferring the sample to the vessel or bomb, by carefully adding the 6 ml of concentrated
nitric acid and 4 ml of concentrated hydrofluoric acid and then continuing to follow the procedures
described in section 3.1.5.3.1; then combine the resultant sample directly with the acid digested portions
of the filter prepared previously in section 3.1.5.3.1. The resultant combined sample is referred to as
Fraction 1 precursor. Filter the combined solution of the acid digested filter and probe rinse samples using
Whatman 541 filter paper. Dilute to 300 ml (or the appropriate volume for the expected metals
concentration) with water. This dilution is Fraction 1. Measure and record the volume of the Fraction 1
solution to within 0.1 ml. Quantitatively remove a 50-ml aliquot and label as Fraction 1B. Label the
remaining 250-ml portion as Fraction 1A. Fraction 1A is used for ICAP or AAS analysis. Fraction 1B is
used for the determination of front-half mercury.

          3.1.5.3.4 Container No. 4 (Impingers 1-3). Measure and record the total volume of this sample
(Fraction 2) to within 0.5 ml. Remove a 75- to 100-ml aliquot for mercury analysis and label as Fraction
2B. Label the remaining portion of Container No. 4 as aliquot Fraction 2A. Aliquot Fraction 2A defines the
volume of 2A prior to digestion. All of the aliquot Fraction 2A is digested to produce concentrated Fraction
2A. Concentrated Fraction 2A defines the volume of 2A after digestion which is normally 150 ml. Only
concentrated Fraction 2A is analyzed for metals (except that it is not analyzed for mercury). The Fraction
2B aliquot should be prepared and analyzed for mercury as described in section 3.1.5.4.3. Aliquot
Fraction 2A shall be pH 2 or lower. If necessary, use concentrated nitric acid, by careful addition and
stirring, to lower aliquot Fraction 2A to pH 2. The sample should be rinsed into a beaker with water and
the beaker should be covered with a ribbed watchglass. The sample volume should be reduced to
approximately 20 ml by heating on a hot plate at a temperature just below boiling. Next follow either the
conventional or microwave digestion procedures described in sections 3.1.5.3.4.1 and 3.1.5.3.4.2, below.

         3.1.5.3.4.1 Conventional Digestion Procedure. Add 30 ml of 50 percent nitric acid and heat for 30
minutes on a hot plate to just below boiling. Add 10 ml of 3 percent hydrogen peroxide and heat for 20
more minutes. Add 50 ml of hot water and heat the sample for an additional 20 minutes. Cool, filter the
sample, and dilute to 150 ml (or the appropriate volume for the expected metals concentrations) with
water. This dilution is concentrated Fraction 2A. Measure and record the volume of the Fraction 2A
solution to within 0.1 ml.

       3.1.5.3.4.2 Microwave Digestion Procedure. Add 10 ml of 50 percent nitric acid and heat for 6
minutes in intervals of 1 to 2 minutes at 600 Watts. Allow the sample to cool. Add 10 ml of 3 percent
hydrogen peroxide and heat for 2 more minutes. Add 50 ml of hot water and heat for an additional 5
minutes. Cool, filter the sample, and dilute to 150 ml (or the appropriate volume for the expected metals
concentrations) with water. This dilution is concentrated Fraction 2A. Measure and record the volume of
the Fraction 2A solution to within 0.1 ml.

         Note: All microwave heating times given are approximate and are dependent upon the number of
samples being digested at a time. Heating times as given above have been found acceptable for
simultaneous digestion of up to 12 individual samples. Sufficient heating is evidenced by solvent reflux
within the vessel.

        3.1.5.3.5 Container Nos. 5A, 5B, and 5C (Impingers 4, 5, and 6). Keep these samples separate
from each other and measure and record the volumes of 5A and 5B separately to within 0.5 ml. Dilute
sample 5C to 500 ml with water. These samples 5A, 5B, and 5C are referred to respectively as Fractions
3A, 3B, and 3C. Follow the analysis procedures described in section 3.1.5.4.3.

         Because the permanganate rinse and water rinse have the capability to recover a high
percentage of the mercury from the permanganate impingers, the amount of mercury in the HCl rinse
(Fraction 3C) may be very small, possibly even insignificantly small. However, as instructed in this
method, add the total of any mercury measured in and calculated for the HCl rinse (Fraction 3C) to that
for Fractions 1B, 2B, 3A, and 3B for calculation of the total sample mercury concentration.

        3.1.5.3.6 Container No. 6 (Silica Gel). Weigh the spent silica gel (or silica gel plus impinger) to the
nearest 0.5 g using a balance. (This step may be conducted in the field.)

        3.1.5.4 Sample Analysis. For each sampling train, seven individual samples are generated for
analysis. A schematic identifying each sample and the prescribed sample preparation and analysis
scheme is shown in Figure 3.1-3. The first two samples, labeled Fractions 1A and 1B, consist of the
digested samples from the front half of the train. Fraction 1A is for ICAP or AAS analysis as described in
sections 3.1.5.4.1 and/or 3.1.5.4.2. Fraction 1B is for determination of front-half mercury as described in
section 3.1.5.4.3.

        The back half of the train was used to prepare the third through seventh samples. The third and
fourth samples, labeled Fractions 2A and 2B, contain the digested samples from the moisture knockout, if
used, and HNO3/H2O2 Impingers 1 through 3. Fraction 2A is for ICAP or AAS analysis. Fraction 2B will be
analyzed for mercury.

        The fifth through seventh samples, labeled Fractions 3A, 3B, and 3C, consist of the impinger
contents and rinses from the empty and permanganate impingers 4, 5, and 6. These samples are
analyzed for mercury as described in section 3.1.5.4.3. The total back-half mercury catch is determined
from the sum of Fraction 2B and Fractions 3A, 3B, and 3C.

         3.1.5.4.1 ICAP Analysis. Fraction 1A and Fraction 2A are analyzed by ICAP using EPA SW-846
method 6010 or method 200.7 (40 CFR 136, appendix C). Calibrate the ICAP, and set up an analysis
program as described in method 6010 or method 200.7. The quality control procedures described in
section 3.1.7.3.1 of this method shall be followed. Recommended wavelengths for use in the analysis are
listed below:



Element                                                  Wavelength (nm)


Aluminum                                                 308.215
Antimony                                                 206.833
Arsenic                                                  193.696
Barium                                                   455.403
Beryllium                                                313.042
Cadmium                                                  226.502
Chromium                                                 267.716
Copper                                                    324.754
Iron                                                      259.940
Lead                                                      220.353
Manganese                                                 257.610
Nickel                                                    231.604
Phosphorus                                                214.914
Selenium                                                  196.026
Silver                                                    328.068
Thallium                                                  190.864
Zinc                                                      213.856



The wavelengths listed are recommended because of their sensitivity and overall acceptance. Other
wavelengths may be substituted if they can provide the needed sensitivity and are treated with the same
corrective techniques for spectral interference.

        Initially, analyze all samples for the desired target metals (except mercury) plus iron and
aluminum. If iron and aluminum are present in the sample, the sample may have to be diluted so that
each of these elements is at a concentration of less than 50 ppm to reduce their spectral interferences on
arsenic, cadmium, chromium, and lead.

         Note. When analyzing samples in a hydrofluoric acid matrix, an alumina torch should be used;
since all front-half samples will contain hydrofluoric acid, use an alumina torch.

        3.1.5.4.2 AAS by Direct Aspiration and/or Graphite Furnace. If analysis of metals in Fraction 1A
and Fraction 2A using graphite furnace or direct aspiration AAS is desired, Table 3.1-2 should be used to
determine which techniques and methods should be applied for each target metal. Table 3.1-2 should
also be consulted to determine possible interferences and techniques to be followed for their
minimization. Calibrate the instrument according to section 3.1.6.3 and follow the quality control
procedures specified in section 3.1.7.3.2.

Table 3.1-2-Applicable Techniques, Methods, and Minimization of Interference for AAS Analysis



                                                                             Interferences


                                       SW-846             Wavelength
Metal               Technique          Method No.         (nm)
                                                                              Cause             Minimization



Sb                  Aspiration         7040               217.6               1000 mg/mL Pb     Use secondary
                                                                              Ni, Cu, or acid   wavelength of
                                                                                                231.1 nm; match
                                                                                                sample &
                                                                                                standards' acid
                                                                                                concentration or
                                                                                                use nitrous
                                                                                                oxide/acetylene
                                                                                                flame.
Sb                  Furnace            7041               217.6               High Pb           Secondary
                                                                                                wavelength or
                                                                                                Zeeman
                                                                                                correction.
As                  Furnace            7060               193.7               Arsenic           Spiked samples
                                 volatization         and add nickel
                                                      nitrate solution
                                                      to digestates
                                                      prior to analysis.
                                 Aluminum             Use Zeeman
                                                      background
                                                      correction.
Ba   Aspiration   7080   553.6   Calcium              High hollow
                                                      cathode current
                                                      and narrow band
                                                      set.
                                 Barium ionization    2 mL of KC1 per
                                                      100 mL of
                                                      sample.
Be   Aspiration   7090   234.9   500 ppm A1           Add 0.1%
                                                      fluoride.
                                 High Mg and Si       Use method of
                                                      standard
                                                      additions.
Be   Furnace      7091   234.9   Be in optical path   Optimize
                                                      parameters to
                                                      minimize effects.
Cd   Aspiration   7130   228.8   Absorption and       Background
                                 light scattering     correction is
                                                      required.
Cd   Furnace      7131   228.8   As above             As above.
                                 Excess chloride      Ammonium
                                                      phosphate used
                                                      as a matrix
                                                      modifier.
                                 Pipet tips           Use
                                                      cadmium-free
                                                      tips.
Cr   Aspiration   7190   357.9   Alkali metal         KC1 ionization
                                                      suppressant in
                                                      samples and
                                                      standards.
                                 Absorption and       Consult
                                 scatter              manufacturer's
                                                      literature.
Cr   Furnace      7191   357.9   200 mg/L Ca and      All calcium
                                 P                    nitrate for a
                                                      known constant
                                                      effect and to
                                                      eliminate effect
                                                      of phosphate.
Cu   Aspiration   7210   324.7   Absorption and       Consult
                                 scatter              manufacturer's
                                                      manual.
Fe   Aspiration   7380   248.3   Contamination        Great care taken
                                                      to avoid
                                                      contamination.
Pb   Aspiration   7420   283.3   217.0 nm             Background
                                 alternate            correction
                                                      required.
Pb   Furnace      7421   283.3   Poor recoveries      Matrix modifier,
                                                      add 10 uL of
                                                      phosphorus acid
                                                      to 1 mL of
                                                      prepared sample
                                                      in sampler cup.
Mn
Aspiration
7460
279.5
                                                      403.1 nm
                                                      alternate
 Background correction       Ni   Aspiration   7520    232.0      352.4 nm
 required.                                                        alternate
 Background correction                                            Fe, Co, and Cr
 required.
 Matrix matching or                                               Nonlinear
 nitrous-oxide/acetylene                                          response
 flame.
 Sample dilution or use      Se   Furnace      7740   196.0       Volatility
 352.3 nm line.
 Spike samples and                                                Adsorption &
 reference materials and                                          scatter
 add nickel nitrate to
 minimize volatilization.
 Background correction       Ag   Aspiration   7760   328.1       Adsorption &
 is required and Zeeman                                           scatter
 background correction
 can be useful.
 Background correction                                            AgC1 insolube
 is required.
 Avoid hydrochloric acid                                          Viscosity
 unless silver is in
 solution as a chloride
 complex.
 Sample and standards        Tl   Aspiration   7840   276.8
 monitored for aspiration
 rate.
 Background correction       Tl   Furnace      7841   276.8       Hydrochloric
 is required.                                                     acid or chloride
 Hydrochloric acid
 should not be used.
 Background correction       Zn   Aspiration   7950   213.9       High Si, Cu, & P
 is required. Verify that
 losses are not
 occurring for
 volatization by spiked
 samples or standard
 addition; Palladium is a
 suitable matrix modifier.
Strontium removes Cu
and phosphate.




Contamination
Great care taken
to avoid
contamination.




                                                                             3.1.5.4.3 Cold Vapor AAS
Mercury Analysis. Fraction 1B, Fraction 2B, and Fractions 3A, 3B, and 3C should be analyzed separately
for mercury using cold vapor atomic absorption spectroscopy following the method outlined in EPA
SW-846 method 7470 or in Standard Methods for Water and Wastewater Analysis, 15th Edition, Method
303F. Set up the calibration curve (zero to 1000 ng) as described in SW-846 method 7470 or similar to
method 303F, using 300-ml BOD bottles instead of Erlenmeyers. Dilute separately, as described below, a
1 ml to 10 ml aliquot of each original sample to 100 ml with water. Record the amount of the aliquot used
for dilution to 100 ml. If no prior knowledge exists of the expected amount of mercury in the sample, a
5-ml aliquot is suggested for the first dilution to 100 ml and analysis. To determine the stack emission
value for mercury, the amount of the aliquot of the sample used for dilution and analysis is dependent on
the amount of mercury in the aliquot: The total amount of mercury in the aliquot used for analysis shall be
less than 1 g, and within the range (zero to 1000 ng) of the calibration curve. Place each sample aliquot
into a separate 300-ml BOD bottle and add enough Type II water to make a total volume of 100 ml. Then
analyze the 100 ml for mercury by adding to it sequentially the sample preparation solutions and
performing the sample preparation and analysis as described in the procedures of SW-846 method 7470
or method 303F. If, during the described analysis, the reading maximum(s) are off-scale (because the
aliquot of the original sample analyzed contained more mercury than the maximum of the calibration
range) including the analysis of the 100-ml dilution of the 1-ml aliquot of the original sample causing a
reading maximum which is off-scale, then perform the following: Dilute the original sample (or a portion of
it) with 0.15% HNO3 in water (1.5 ml concentrated HNO3 per liter aqueous solution) so that when a 1-ml to
10-ml aliquot of the dilution of the original sample is then further diluted to 100 ml in the BOD bottle, and
analyzed by the procedures described above, it will yield an analysis within the range of the calibration
curve.

3.1.6 Calibration

                                                                         Maintain a laboratory log of all
calibrations.

                                                                        3.1.6.1 Sampling Train
Calibration. Calibrate the sampling train components according to the indicated sections of method 5:
Probe Nozzle (section 5.1); Pitot Tube (section 5.2); Metering System (section 5.3); Probe Heater (section
5.4); Temperature Gauges (section 5.5); Leak-Check of the Metering System (section 5.6); and
Barometer (section 5.7).

                                                                       3.1.6.2 Inductively Coupled Argon
Plasma Spectrometer Calibration. Prepare standards as outlined in section 3.1.4.4. Profile and calibrate
the instrument according to the instrument manufacturer's recommended procedures using the above
standards. The instrument calibration should be checked once per hour. If the instrument does not
reproduce the concentrations of the standard within 10 percent, the complete calibration procedures
should be performed.

                                                                         3.1.6.3 Atomic Absorption
Spectrometer-Direct Aspiration, Graphite Furnace and Cold Vapor Mercury Analyses. Prepare the
standards as outlined in section 3.1.4.4. Calibrate the spectrometer using these prepared standards.
Calibration procedures are also outlined in the EPA methods referred to in Table 3.1-2 and in SW-846
Method 7470 or Standard Methods for Water and Wastewater, 15th Edition, method 303F (for mercury).
Each standard curve should be run in duplicate and the mean values used to calculate the calibration
line. The instrument should be recalibrated approximately once every 10 to 12 samples.

3.1.7 Quality Control

                                                                           3.1.7.1 Sampling. Field Reagent
Blanks. When analyzed, the blank samples in Container Numbers 7 through 12 produced previously in
sections 3.1.5.2.7 through 3.1.5.2.12, respectively, shall be processed, digested, and analyzed as follows:
Digest and process one of the filters from Container No. 12 per section 3.1.5.3.1, 100 ml from Container
No. 7 per section 3.1.5.3.2, and 100 ml from Container No. 8A per section 3.1.5.3.3. This produces
Fraction Blank 1A and Fraction Blank 1B from Fraction Blank 1. (If desired, the other two filters may be
digested separately according to section 3.1.5.3.1, diluted separately to 300 ml each, and analyzed
separately to produce a blank value for each of the two additional filters. If these analyses are performed,
they will produce two additional values for each of Fraction Blank 1A and Fraction Blank 1B. The three
Fraction Blank 1A values will be calculated as three values of Mfhb in Equation 3 of section 3.1.8.4.3, and
then the three values shall be totalled and divided by 3 to become the value M fhb to be used in the
computation of Mt by Equation 3. Similarly, the three Fraction Blank 1B values will be calculated
separately as three values, totalled, averaged, and used as the value for Hg fhb in Equation 8 of section
3.1.8.5.3. The analyses of the two extra filters are optional and are not a requirement of this method, but if
the analyses are performed, the results must be considered as described above.) Combine 100 ml of
Container No. 8A with 200 ml of the contents of Container No. 9 and digest and process the resultant
volume per section 3.1.5.3.4. This produces concentrated Fraction Blank 2A and Fraction Blank 2B from
Fraction Blank 2. A 100-ml portion of Container No. 8A is Fraction Blank 3A. Combine 100 ml of the
contents of Container No. 10 with 33 ml of the contents of Container No. 8B. This produces Fraction
Blank 3B (use 400 ml as the volume of Fraction Blank 3B when calculating the blank value. Use the
actual volumes when calculating all the other blank values). Dilute 225 ml of the contents of Container
No. 11 to 500 ml with water. This produces Fraction Blank 3C. Analyze Fraction Blank 1A and Fraction
Blank 2A per section 3.1.5.4.1 and/or 3.1.5.4.2. Analyze Fraction Blank 1B, Fraction Blank 2B, and
Fraction Blanks 3A, 3B, and 3C per section 3.1.5.4.3. The analysis of Fraction Blank 1A produces the
front-half reagent blank correction values for the metals except mercury; the analysis of Fraction Blank 1B
produces the front-half reagent blank correction value for mercury. The analysis of concentrated Fraction
Blank 2A produces the back-half reagent blank correction values for the metals except mercury, while
separate analysis of Fraction Blanks 2B, 3A, 3B, and 3C produce the back-half reagent blank correction
value for mercury.

                                                                         3.1.7.2 An attempt may be made
to determine if the laboratory reagents used in section 3.1.5.3 caused contamination. They should be
analyzed by the procedures in section 3.1.5.4. The Administrator will determine whether the laboratory
blank reagent values can be used in the calculation of the stationary source test results.

                                                                          3.1.7.3 Quality Control Samples.
The following quality control samples should be analyzed.

                                                                        3.1.7.3.1 ICAP Analysis. Follow
the quality control shown in section 8 of method 6010. For the purposes of a three-run test series, these
requirements have been modified to include the following: Two instrument check standard runs, two
calibration blank runs, one interference check sample at the beginning of the analysis (must be within
25% or analyze by the method of standard additions), one quality control sample to check the accuracy of
the calibration standards (must be within 25% of calibration), and one duplicate analysis (must be within
10% of average or repeat all analyses).

                                                                          3.1.7.3.2 Direct Aspiration and/or
Graphite Furnace AAS Analysis for antimony, arsenic, barium, beryllium, cadmium, copper, chromium,
lead, nickel, manganese, mercury, phosphorus, selenium, silver, thallium, and zinc. All samples should be
analyzed in duplicate. Perform a matrix spike on at least one front-half sample and one back-half sample
or one combined sample. If recoveries of less than 75 percent or greater than 125 percent are obtained
for the matrix spike, analyze each sample by the method of standard additions. A quality control sample
should be analyzed to check the accuracy of the calibration standards. The results must be within 10% or
the calibration repeated.

                                                                        3.1.7.3.3 Cold Vapor AAS
Analysis for Mercury. All samples should be analyzed in duplicate. A quality control sample should be
analyzed to check the accuracy of the calibration standards (within 15% or repeat calibration). Perform a
matrix spike on one sample from the nitric impinger portion (must be within 25% or samples must be
analyzed by the method of standard additions). Additional information on quality control can be obtained
from EPA SW-846 method 7470 or in Standard Methods for the Examination of Water and Wastewater,
15th Edition, method 303F.

3.1.8 Calculations

                                                                           3.1.8.1 Dry Gas Volume. Using
the data from this test, calculate Vm(std), the dry gas sample volume at standard conditions as outlined in
Section 6.3 of Method 5.

                                                                         3.1.8.2 Volume of Water Vapor
and Moisture Content. Using the data obtained from this test, calculate the volume of water vapor V w(std)
and the moisture content Bws of the stack gas. Use Equations 5-2 and 5-3 of Method 5.

                                                                        3.1.8.3 Stack Gas Velocity. Using
the data from this test and Equation 2-9 of Method 2, calculate the average stack gas velocity.

                                                                             3.1.8.4 Metals (Except Mercury)
in Source Sample.

                                                                       3.1.8.4.1 Fraction 1A, Front Half,
Metals (except Hg). Calculate separately the amount of each metal collected in Fraction 1 of the sampling
train using the following equation:

Mfh = Ca1 Fd Vsoln,1
                                                                                     *
                                                                                 Eq. 1
                                                                             *
                                                                     If Fractions 1A and 2A are
combined, proportional aliquots must be used. Appropriate changes must be made in Equations 1-3 to
reflect this approach.

where:

Mfh =                                                                        total mass of each metal (except
                  Hg) collected in the front half of the sampling train (Fraction 1), g.
Ca1 =                                                                        concentration of metal in sample
                  Fraction 1A as read from the standard curve (g/ml).
Fd =                                                                         dilution factor (Fd = the inverse of
                  the fractional portion of the concentrated sample in the solution actually used in the
                  instrument to produce the reading Ca1. For example, when 2 ml of Fraction 1A are diluted
                  to 10 ml, Fd = 5).
Vsoln,1 =         total volume of digested sample solution (Fraction 1), ml.

                                                                       3.1.8.4.2 Fraction 2A, Back Half,
Metals (except Hg). Calculate separately the amount of each metal collected in Fraction 2 of the sampling
train using the following equation:
Mbh =    Ca2FaVa
                                                                                             *
                                                                                     Eq. 2

where:

Mbh =    total mass of each metal (except Hg) collected in the back half of the sampling train (Fraction 2),
         g.
Ca2 =    concentration of metal in sample concentrated Fraction 2A, as read from the standard curve
         (g/ml).
Fa =     aliquot factor, volume of Fraction 2 divided by volume of aliquot Fraction 2A (see section
         3.1.5.3.4).
Va =     total volume of digested sample solution (concentrated Fraction 2A), ml (see section 3.1.5.3.4.1
         or 3.1.5.3.4.2, as applicable).

                                                                         3.1.8.4.3 Total Train, Metals
(except Hg). Calculate the total amount of each of the quantified metals collected in the sampling train as
follows:

Mt =                                                                      (Mfh - Mfhb) + (Mbh - Mbhb)
                                                                                           *
                                                                                     Eq. 3

where:

Mt =                                                                       total mass of each metal
                   (separately stated for each metal) collected in the sampling train, g.
Mfhb =                                                                     blank correction value for mass of
                   metal detected in front-half field reagent blank, g.
Mbhb =                                                                     blank correction value for mass of
                   metal detected in back-half field reagent blank, g.

                                                                          Note: If the measured blank value
for the front half (mfhb) is in the range 0.0 to A g (where A g equals the value determined by
                                                   2                                       2
multiplying 1.4 g per square inch (1.4 g/in ) times the actual area in square inches (in ) of the filter
used in the emission sample) m fhb may be used to correct the emission sample value (m fh); if mfhb
exceeds A g, the greater of the two following values (either I. or II.) may be used:

                                                                          I. A g, or

                                                                          II. the lesser of (a) m fhb, or (b) 5
percent of mfh.

                                                                         If the measured blank value for
the back half (mbhb) is in the range of 0.0 to 1 g, mbhb may be used to correct the emission sample value
(mbh); if mbhb exceeds 1 g, the greater of the two following values may be used: 1 g or 5 percent of
mbh.

                                                                          3.1.8.5 Mercury in Source
Sample.

                                                                          3.1.8.5.1 Fraction 1B, Front Half,
Hg. Calculate the amount of mercury collected in the front half, Fraction 1, of the sampling train using the
following equation:

                                                                              Qfh
Hgfh                                                                      =                      X      Vsoln,1
                                                                                                        Eq. 4
                                                                                Vf1B

where:

Hgfh =              total mass of mercury collected in the front half of the sampling train (Fraction 1), g.
Qfh =               quantity of mercury in analyzed sample, g.
Vsoln,1 =           total volume of digested sample solution (Fraction 1), ml.
Vf1B =              volume of Fraction 1B analyzed, ml.

            See the following notice.

         Note: Vf1B is the actual amount of Fraction 1B analyzed. For example, if 1 ml of Fraction lB were
diluted to 100 ml to bring it into the proper analytical range, and 1 ml of the 100-ml dilution were analyzed,
Vf1B would be 0.01 ml.

        3.1.8.5.2 Fraction 2B and Fractions 3A, 3B, and 3C, Back Half, Hg. Calculate the amount of
mercury collected in Fractions 2 using Equation 5 and in Fractions 3A, 3B, and 3C using Equation 6.
Calculate the total amount of mercury collected in the back half of the sampling train using Equation 7.

                    Qbh2
Hgbh2       =                            X   Vsoln,2                                              Eq. 5

                    Vf2B

where:

Hgbh2 =           total mass of mercury collected in Fraction 2, g.
Qbh2 =                     quantity of mercury in analyzed sample, g.
Vsoln,2 =         total volume of Fraction 2, ml.
Vf2B =                     volume of Fraction 2B analyzed, ml (see the following note).
         Note: Vf2B is the actual amount of Fraction 2B analyzed. For example, if 1 ml of Fraction 2B were
diluted to 10 ml to bring it into the proper analytical range, and 5 ml of the 10-ml dilution was analyzed,
Vf2B would be 0.5.

            Use Equation 6 to calculate separately the back-half mercury for Fractions 3A, then 3B, then 3C.

                            Qbh3(A,B,C)
Hgbh3(A,B,C)        =                                  X       Vsoln,3(A,B,C)                     Eq.6

                            Vf3(A,B,C)

where:

Hgbh3(A,B,C) =      total mass of mercury collected separately in Fraction 3A, 3B, or 3C, g.
Qbh3(A,B,C) =                         quantity of mercury in separately analyzed samples, g.
Vf3(A,B,C) =                          volume of Fraction 3A, 3B, or 3C analyzed, ml (see Note in sections
                             3.1.8.5.1 and 3.1.8.5.2, and calculate similarly).
Vsoln,3(A,B,C) =    total volume of Fraction 3A, 3B, or 3C, ml.

Hgbh =              Hgbh2 + Hgbh3A + Hgbh3B + Hgbh3C                            Eq. 7

where:

Hgbh =              total mass of mercury collected in the back half of the sampling train, g.
       3.1.8.5.3 Total Train Mercury Catch. Calculate the total amount of mercury collected in the
sampling train using Equation 8.

Hgt =                        (Hgfh - Hgfhb) + (Hgbh - Hgbhb)                                     Eq. 8

where:

Hgt =                        total mass of mercury collected in the sampling train, g.
Hgfhb =              blank correction value for mass of mercury detected in front-half field reagent blank, g.
Hgfhb =              blank correction value for mass of mercury detected in back-half field reagent blanks,
                     g.

         Note: If the total of the measured blank values (Hgfhb + Hgbhb) is in the range of 0 to 6 g, then
the total may be used to correct the emission sample value (Hgfh + Hgbh); if it exceeds 6 g, the greater
of the following two values may be used; 6 g or 5 percent of the emission sample value (Hgfh + Hgbh).

        3.1.8.6 Metal Concentration of Stack Gas. Calculate each metal separately for the cadmium, total
chromium, arsenic, nickel, manganese, beryllium, copper, lead, phosphorus, thallium, silver, barium, zinc,
selenium, antimony, and mercury concentrations in the stack gas (dry basis, adjusted to standard
conditions) as follows:

Cs =        K4(Mt/Vm(std))                                                              Eq. 9

where:

Cs =                          concentration of each metal in the stack gas, mg/dscm.
                                 -3
K4 =                          10 mg/g.
Mt =                          total mass of each metal collected in the sampling train, g; (substitute Hgt for Mt
                     for the mercury calculation).
Vm(std) =            volume of gas sample as measured by the dry gas meter, corrected to dry standard
                     conditions, dscm.

        3.1.8.7 Isokinetic Variation and Acceptable Results. Same as method 5, sections 6.11 and 6.12,
respectively.

3.1.9 Bibliography

         3.1.9.1 Method 303F in Standard Methods for the Examination of Water and Wastewater, 15th
Edition, 1980. Available from the American Public Health Association. 1015 18th Street NW., Washington,
DC 20036.

         3.1.9.2 EPA Methods 6010, 7000, 7041, 7060, 7131, 7421. 7470, 7740. and 7841. Test Methods
for Evaluating Solid Waste: Physical/Chemical Methods SW-846, Third Edition. September 1988. Office
of Solid Waste and Emergency Response, U.S. Environmental Protection Agency, Washington, DC
20460.

            3.1.9.3 EPA Method 200.7, Code of Federal Regulations, title 40, part 136, appendix C. July 1,
1987.

         3.1.9.4 EPA Methods 1 through 5, and 12 Code of Federal Regulations, title 40, part 60, appendix
A, July 1, 1987.
                                                                                                  +6
3.2 Determination of Hexavalent Chromium Emissions from Stationary Sources (Method Cr )

3.2.1 Applicability and Principle
                                                                                                     +6
        3.2.1.1 Applicability. This method applies to the determination of hexavalent chromium (Cr )
emissions from hazardous waste incinerators. municipal waste combustors, sewage sludge incinerators,
and boilers and industrial furnaces. With the approval of the Administrator, this method may also be used
to measure total chromium. The sampling train, constructed of Teflon components, has only been
evaluated at temperatures less than 300 F. Trains constructed of other materials, for testing at higher
temperatures, are currently being evaluated.
                                                                   +6
         3.2.1.2 Principle. For incinerators and combustors, the Cr emissions are collected isokinetically
                                                   +6
from the source. To eliminate the possibility of Cr reduction between the nozzle and impinger, the
emission samples are collected with a recirculatory train where the impinger reagent is continuously
recirculated to the nozzle. Recovery procedures include a post- sampling purge and filtration. The
                                              +6
impinger train samples are analyzed for Cr by an ion chromatograph equipped with a post-column
                                                                           +6                   4+6=
reactor and a visible wavelength detector. The IC/PCR separates the Cr as chromate (CrO              ) from
                                                                          +6
other components in the sample matrices that may interfere with the Cr -specific diphenylcarbazide
reaction that occurs in the post-column reactor. To increase sensitivity for trace levels of chromium, a
preconcentration system is also used in conjunction with the IC/PCR.

3.2.2 Range, Sensitivity, Precision, and Interference

        3.2.2.1 Range. Employing a preconcentration procedure, the lower limit of the detection range
can be extended to 16 nanograms per dry standard cubic meter (ng/dscm) with a 3 dscm gas sample (0.1
ppb in solution). With sample dilution, there is no upper limit.

       3.2.2.2 Sensitivity. A minimum detection limit of 8 ng/dscm with a 3 dscm gas sample can be
achieved by preconcentration (0.05 ppb in solution).

         3.2.2.3 Precision. The precision of the IC/PCR with sample preconcentration is 5 to 10 percent.
                                                                               +6
The overall precision for sewage sludge incinerators emitting 120 ng/dscm of Cr and 3.5 g/dscm of
                                      +6
total chromium is 25% and 9% for Cr and total chromium, respectively; for hazardous waste incinerators
                             +6
emitting 300 ng/dscm of Cr it is 20 percent.
                                                                               +6
         3.2.2.4 Interference. Components in the sample matrix may cause Cr to convert to trivalent
               +3             +3                +6
chromium (Cr ) or cause Cr to convert to Cr        A post-sampling nitrogen purge and sample filtration
                                                                                             +6
are included to eliminate many of these interferences. The chromatographic separation of Cr using ion
chromatography reduces the potential for other metals to interfere with the post-column reaction. For the
                                                       +6
IC/PCR analysis, only compounds that coelute with Cr and affect the diphenylcarbazide reaction will
cause interference. Periodic analysis of deionized (DI) water blanks is used to demonstrate that the
analytical system is essentially free from contamination. Sample cross-contamination that can occur when
high-level and low-level samples or standards are analyzed alternately is eliminated by thorough purging
of the sample loop. Purging can easily be achieved by increasing the injection volume of the samples to
ten times the size of the sample loop.

3.2.3 Apparatus

        3.2.3.1 Sampling Train. Schematics of the recirculating sampling trains employed in this method
are shown in Figures 3.2-1 and 3.2-2. The recirculatory train is readily assembled from commercially
available components. All portions of the train in contact with the sample are either glass, quartz, Tygon,
or Teflon, and are to be cleaned as per subsection 3.2.5.1.1.

         The metering system is identical to that specified by Method 5 (see section 3.8.1); the sampling
train consists of the following components:

>>>> See the accompanying hardcopy volume for non-machine-readable data that appears at this point.
<<<<
         3.2.3.1.1 Probe Nozzle. Glass or Teflon with a sharp, tapered leading edge. The angle of taper
shall be 30 and the taper shall be on the outside to preserve a constant internal diameter. The probe
nozzle shall be of the button-hook or elbow design, unless otherwise specified by the Administrator.

         A range of nozzle sizes suitable for isokinetic sampling should be available, e.g., 0.32 to 1.27 cm
( 1/8 to 1/2 in) (or larger if higher volume sample trains are used) inside diameter (ID) nozzles in
increments of 0.16 cm ( 1/16 in). Each nozzle shall be calibrated according to the procedures outlined in
section 3.2.6.

         3.2.3.1.2 Teflon Aspirator or Pump/Sprayer Assembly. Teflon aspirator capable of recirculating
absorbing reagent at 50 ml/min while operating at 0.75 cfm. Alternatively, a pump/sprayer assembly may
be used instead of the Teflon aspirator. A Teflon union-T is connected behind the nozzle to provide the
absorbing reagent/sample gas mix; a peristaltic pump is used to recirculate the absorbing reagent at a
flow rate of at least 50 ml/min. Teflon fittings, Teflon ferrules. and Teflon nuts are used to connect a glass
                                                                                                        **
or Teflon nozzle. recirculating line. and sample line to the Teflon aspirator or union-T. Tygon, C-flex or
other suitable inert tubing for use with peristaltic pump.
        *
        Note: Mention of trade names or specific product does not constitute endorsement by the
Environmental Protection Agency.

       3.2.3.1.3 Teflon Sample Line. Teflon, 3/8" outside diameter (OD) and 1/4" inside diameter (ID),
or 1/2" OD x 3/8" ID, of suitable length to connect aspirator (or T-union) to first Teflon impinger.

         3.2.3.1.4 Teflon Recirculation Line. Teflon, 1/4" O.D. and 1/8" I.D., of suitable length to connect
first impinger to aspirator (or T-union).

          3.2.3.1.5 Teflon Impingers. Four Teflon Impingers; Teflon tubes and fittings, such as made by
         **
Savillex can be used to construct impingers 2" diameter by 12" long, with vacuum-tight 3/8" O.D. Teflon
compression fittings. Alternatively, standard glass impingers that have been Teflon-lined, with Teflon
stems and U-tubes, may be used. Inlet fittings on impinger top to be bored through to accept 3/8" O.D.
tubing as impinger stem. The second and third 3/8" OD Teflon stem has a 1/4" OD Teflon tube, 2" long.
inserted at its end to duplicate the effects of the Greenburg-Smith impinger stem. The first impinger stem
should extend 2" from impinger bottom, high enough in the impinger reagent to prevent air from entering
recirculating line; the second and third impinger stems should extent to 1/2" from impinger bottom. The
first impinger should include a 1/4" O.D. Teflon compression fitting for recirculation line. The fourth
impinger serves as a knockout impinger.

          3.2.3.1.6 Glass Impinger. Silica gel impinger. Vacuum-tight impingers, capable of containing 400
g of silica gel, with compatible fittings. The silica gel impinger will have a modified stem ( 1/2" ID at tip of
stem).

       3.2.3.1.7 Thermometer, (identical to that specified by Method 5) at the outlet of the silica gel
impinger, to monitor the exit temperature of the gas.

       3.2.3.1.8 Metering System, Barometer, and Gas Density Determinations Equipment. Same as
method 5, sections 2.1.8 through 2.1.10, respectively.

         3.2.3.2 Sample Recovery. Clean all items for sample handling or storage with 10% nitric acid
solution by soaking, where possible, and rinse thoroughly with DI water before use.

         3.2.3.2.1 Nitrogen Purge Line. Inert tubing and fittings capable of delivering 0 to 1 scf/min
(continuously adjustable) of nitrogen gas to the impinger train from a standard gas cylinder (see Figure
3.2.3). Standard 3/8-inch Teflon tubing and compression fittings in conjunction with an adjustable
pressure regulator and needle valve may be used.
>>>> See the accompanying hardcopy volume for non-machine-readable data that appears at this point.
<<<<

        3.2.3.2.2 Wash bottles. Two polyethylene wash bottles, for DI water and nitric rinse solution.

        3.2.3.2.3 Sample Storage Containers. Polyethylene, with leak-free screw cap, 500-ml or 1000-ml.

        3.2.3.2.4 1000-ml Graduated Cylinder.

        3.2.3.2.5 Plastic Storage Containers. Air tight containers to store silica gel.

        3.2.3.2.6 Funnel and Rubber Policeman. To aid in transfer of silica gel from impinger to storage
container; not necessary if silica gel is weighed directly in the impinger.

        3.2.3.2.7 Balance.

         3.2.3.3 Sample Preparation for Analysis. Sample preparation prior to analysis includes purging
the sample train immediately following the sample run. and filtering the recovered sample to remove
particulate matter immediately following recovery.

        3.2.3.3.1 Beakers, Funnels, Volumetric Flasks, Volumetric Pipets, and Graduated Cylinders.
Assorted sizes, Teflon or glass, for preparation of samples, sample dilution, and preparation of calibration
standards. Prepare initially following procedure described in section 3.2.5.1.3 and rinse between use with
0.1 N HNO3 and DI water.

          3.2.3.3.2 Filtration Apparatus. Teflon, or equivalent, for filtering samples, and Teflon filter holder.
Teflon impinger components have been found to be satisfactory as a sample reservoir for pressure
filtration using nitrogen.

         3.2.3.4 Analysis.
         3.2.3.4.1 IC/PCR System. High performance liquid chromatograph pump, sample injection valve,
post-column reagent delivery and mixing system, and a visible detector, capable of operating at 520 nm,
all with a non-metallic (or inert) flow path. An electronic recording integrator operating in the peak area
mode is recommended, but other recording devices and integration techniques are acceptable provided
the repeatability criteria and the linearity criteria for the calibration curve described in section 3.2.5.5 can
be satisfied. A sample loading system will be required if preconcentration is employed.

        3.2.3.4.2 Analytical Column. A high performance ion chromatograph (HPIC) non-metallic column
with anion separation characteristics and a high loading capacity designed for separation of metal
chelating compounds to prevent metal interference. Resolution described in section 3.2.5.4 must be
obtained. A non-metallic guard column with the same ion-exchange material is recommended.

        3.2.3.4.3 Preconcentration Column. An HPIC non-metallic column with acceptable anion retention
characteristics and sample loading rates as described in section 3.2.5.5.

       3.2.3.4.4 0.45 um filter cartridge. For the removal of insoluble material. To be used just prior to
sample injection/analysis.

3.2.4 Reagents

        All reagents should, at a minimum, conform to the specifications established by the Committee on
Analytical Reagents of the American Chemical Society, where such specifications are available. All
                                                                        +6
prepared reagents should be checked by IC/PCR analysis for Cr to ensure that contamination is below
the analytical detection limit for direct injection or, if selected, preconcentration. If total chromium is also to
be determined, the reagents should also be checked by the analytical technique selected to ensure that
contamination is below the analytical detection limit.
        3.2.4.1 Sampling.

        3.2.4.1.1 Water. Deionized water. It is recommended that water blanks be checked prior to
                                                   +6
preparing sampling reagents to ensure that the Cr content is less than the analytical detection limit.

         3.2.4.1.2 Potassium Hydroxide, 0.1 N. Add 5.6 gm of KOH(s) to approximately 900 ml of DI water
and let dissolve. Dilute to 1000 ml with DI water.

        Note: At sources with high concentrations of acids and/or SO 2, the concentration of KOH should
be increased to 0.5 N to ensure that the pH of the solution is above 8.5 after sampling.

        3.2.4.1.3 Silica Gel and Crushed Ice. Same as Method 5, sections 3.1.2 and 3.1.4, respectively.

        3.2.4.2 Sample Recovery. The reagents used in sample recovery are as follows:

        3.2.4.2.1 Water. Same as subsection 3.2.4.1.1.

        3.2.4.2.2 Nitric Acid, 0.1 N. Add 6.3 ml of concentrated HNO 3 (70 percent) to a graduated cylinder
containing approximately 900 ml of DI water. Dilute to 1000 ml with DI water, and mix well.

        3.2.4.2.3 pH Indicator Strip. pH indicator capable of determining pH of solution between the pH
range of 7 and 12, at 0.5 pH intervals.

        3.2.4.3 Sample Preparation

        3.2.4.3.1 Water. Same as subsection 3.2.4.1.1.

        3.2.4.3.2 Nitric Acid, 0.1 N. Same as subsection 3.2.4.2.2.

         3.2.4.3.3 Filters. Acetate membrane, or equivalent, filters with 0.45 micrometer or smaller pore
size to remove insoluble material.

        3.2.4.4 Analysis.

         3.2.4.4.1 Chromatographic Eluent. The eluent used in the analytical system is ammonium sulfate
based. It is prepared by adding 6.5 ml of 29 percent ammonium hydroxide (NH 4OH) and 33 grams of
ammonium sulfate ((NH4)2SO4) to 500 ml of DI water. The mixture should then be diluted to 1 liter with DI
water and mixed well. Other combinations of eluents and/or columns may be employed provided peak
resolution, as described in section 3.2.5.4, repeatability and linearity, as described in section 3.2.6.2, and
analytical sensitivity are acceptable.

        3.2.4.4.2 Post-Column Reagent. An effective post-column reagent for use with the
chromatographic eluent described in section 3.2.4.4.1 is a diphenylcarbazide (DPC) based system.
Dissolve 0.5 g of 1.5-diphenylcarbazide (DPC) in 100 ml of ACS grade methanol. Add to 500 ml of
degassed DI water containing 50 ml of 96 percent spectrophotometric grade sulfuric acid. Dilute to 1 liter
with degassed DI water.
                    +6                                   +6
        3.2.4.4.3 Cr Calibration Standard. Prepare Cr standards from potassium dichromate (K2Cr2O7,
                                         +6
FW 294.19). To prepare a 1000 g/ml Cr stock solution, dissolve 2.829 g of dry K2Cr2O7 in 1 liter of DI
water. To prepare working standards, dilute the stock solution to the chosen standard concentrations for
instrument calibration with 0.05 N KOH to achieve a matrix similar to the actual field samples.

        3.2.4.4.4 Performance Audit Sample. A performance audit sample shall be obtained from the
Quality Assurance Division of EPA and analyzed with the field samples. The mailing address to request
audit samples is: U.S. Environmental Protection Agency, Atmospheric Research and Exposure
Assessment Laboratory, Quality Assurance Division, Source Branch. Mail Drop 77-A, Research Triangle
Park, North Carolina 27711.

         The audit sample should be prepared in a suitable sample matrix at a concentration similar to the
actual field samples.

3.2.5 Procedure

Safety First-Wear Safety Glasses at All Times During This Test Method

        3.2.5.1 Sampling. The complexity of this method is such that to obtain reliable results, testers
should be trained and experienced with test procedures.

       3.2.5.1.1 Pretest Preparation. All components shall be maintained and calibrated according to the
procedures described in APTD-0576, unless otherwise specified herein.

          Rinse all sample train components from the glass nozzle up to the silica gel impinger and sample
containers with hot tap water followed by washing with hot soapy water. Next, rinse the train components
and sample containers three times with tap water followed by three rinses with DI water. All the
components and containers should then be soaked overnight, or a minimum of 4 hours, in a 10 percent
(v/v) nitric acid solution, then rinsed three times with DI water. Allow the components to air dry prior to
covering all openings with Parafilm, or equivalent.

        3.2.5.1.2 Preliminary Determinations. Same as method 5, section 4.1.2.

         3.2.5.1.3 Preparation of Sampling Train. Measure 300 ml of 0.1 N KOH into a graduated cylinder
(or tare-weighed precleaned polyethylene container). Place approximately 150 ml of the 0.1 N KOH
reagent in the first Teflon impinger. Split the rest of the 0.1 N KOH between the second and third Teflon
impingers. The next Teflon impinger is left dry. Place a preweighed 200-to 400-g portion of indicating
silica gel in the final glass impinger. (For sampling periods in excess of two hours, or for high moisture
sites. 400-g of silica gel is recommended.)

        Retain reagent blanks of the 0.1 N KOH equal to the volumes used with the field samples.

         3.2.5.1.4 Leak-Check Procedures. Follow the leak-check procedures given in Method 5, section
4.1.4.1 (Pretest Leak-Check), Section 4.1.4.2 (Leak-Checks During the Sample Run), and Section 4.1.4.3
(Post-Test Leak-Checks).

       3.2.5.1.5 Sampling Train Operation. Follow the procedures given in method 5, section 4.1.5. The
sampling train should be iced down with water and ice to ensure heat transfer with the Teflon impingers.

         Note: If the gas to be sampled is above 200 F, it may be necessary to wrap three or four feet of
the Teflon sample and recirculating lines inside the ice bath to keep the recirculated reagent cool enough
so it does not turn to steam.

       For each run, record the data required on a data sheet such as the one shown in Figure 5.2 of
method 5.

         At the end of the sampling run, determine the pH of the reagent in the first impinger using a pH
indicator strip. The pH of the solution shall be greater than 8.5.

        3.2.5.1.6 Calculation of Percent Isokinetic. Same as method 5, section 4.1.6.

        3.2.5.2 Post-Test Nitrogen Purge. The nitrogen purge is used as a safeguard against the
conversion of hexavalent chromium to the trivalent oxidation state. The purge is effective in the removal
of SO2 from the impinger contents.
         Attach the nitrogen purge line to the input of the impinger train. Check to ensure the output of the
impinger train is open, and that the recirculating line is capped off. Open the nitrogen gas flow slowly and
adjust the delivery rate to 10 L/min. Check the recirculating line to ensure that the pressure is not forcing
the impinger reagent out through this line. Continue the purge under these conditions for one-half hour,
periodically checking the flow rate.

         3.2.5.3 Sample Recovery. Begin cleanup procedures as soon as the train assembly has been
purged at the end of the sampling run. The probe assembly may be disconnected from the sample train
prior to sample purging.

         The probe assembly should be allowed to cool prior to sample recovery. Disconnect the umbilical
cord from the sample train. When the probe assembly can be safely handled, wipe off all external
particulate matter near the tip of the nozzle, and cap the nozzle prior to transporting the sample train to a
cleanup area that is clean and protected from the wind and other potential causes of contamination or
loss of sample. Inspect the train before and during disassembly and note any abnormal conditions.

         3.2.5.3.1 Container No. 1 (Impingers 1 through 3). Disconnect the first impinger from the second
impinger and disconnect the recirculation line from the aspirator or peristaltic pump. Drain the Teflon
impingers into a precleaned graduated cylinder or tare-weighed precleaned polyethylene sample
container and measure the volume of the liquid to within 1 ml or 1 g. Record the volume of liquid present
as this information is required to calculate the moisture content of the flue gas sample. If necessary,
transfer the sample from the graduated cylinder to a precleaned polyethylene sample container. With DI
water, rinse four times the insides of the glass nozzle, the aspirator, the sample and recirculation lines,
the impingers, and the connecting tubing, and combine the rinses with the impinger solution in the sample
container.

         3.2.5.3.2 Container No. 2 (HNO3 rinse optional for total chromium). With 0.1 N HNO3, rinse three
times the entire train assembly, from the nozzle to the fourth impinger and combine the rinses into a
separate precleaned polyethylene sample container for possible total chromium analysis. Repeat the
rinse procedure a final time with DI water, and discard the water rinses. Mark the height of the fluid level
on the container or, alternatively if a balance is available, weigh the container and record the weight to
permit determination of any leakage during transport. Label the container clearly to identify its contents.

         3.2.5.3.3 Container No. 3 (Silica Gel). Note the color of the indicating silica gel to determine if it
has been completely spent. Quantitatively transfer the silica gel from its impinger to the original container,
and seal the container. A funnel and a rubber policeman may be used to aid in the transfer. The small
amount of particulate that may adhere to the impinger wall need not be removed. Do not use water or
other liquids to transfer the silica gel. Alternatively, if a balance is available in the field, record the weight
of the spent silica gel (or the silica gel plus impinger) to the nearest 0.5 g.

        3.2.5.3.4 Container No. 4 (0.1 N KOH Blank). Once during each field test, place a volume of
reagent equal to the volume placed in the sample train into a precleaned polyethylene sample container,
and seal the container. Mark the height of the fluid level on the container or, alternatively if a balance is
available, weigh the container and record the weight to permit determination of any leakage during
transport. Label the container clearly to identify its contents.

         3.2.5.3.5 Container No. 5 (DI Water Blank). Once during each field test, place a volume of DI
water equal to the volume employed to rinse the sample train into a precleaned polyethylene sample
container, and seal the container. Mark the height of the fluid level on the container or, alternatively if a
balance is available, weigh the container and record the weight to permit determination of any leakage
during transport. Label the container clearly to identify its contents.

          3.2.5.3.6 Container No. 6 (0.1 N HNO3 Blank). Once during each field test if total chromium is to
be determined, place a volume of 0.1 N HNO3 reagent equal to the volume employed to rinse the sample
train into a pre-cleaned polyethylene sample container, and seal the container. Mark the height of the fluid
level on the container or, alternatively if a balance is available, weigh the container and record the weight
to permit determination of any leakage during transport. Label the container clearly to identify its contents.
                                                                +6
          3.2.5.4 Sample Preparation. For determination of Cr , the sample should be filtered immediately
following recovery to remove any insoluble matter. Nitrogen gas may be used as a pressure assist to the
                                 +6
filtration process (see Figure Cr -4).

         Filter the entire impinger sample through a 0.45-micrometer acetate filter (or equivalent), and
collect the filtrate in a 1000-ml graduated cylinder. Rinse the sample container with DI water three
separate times, pass these rinses through the filter, and add the rinses to the sample filtrate. Rinse the
Teflon reservoir with DI water three separate times, pass these rinses through the filter, and add the
rinses to the sample. Determine the final volume of the filtrate and rinses and return them to the rinsed
polyethylene sample container. Label the container clearly to identify its contents. Rinse the Teflon
reservoir once with 0.1 N HNO3 and once with DI water and discard these rinses.

          If total chromium is to be determined, quantitatively recover the filter and residue and place them
in a vial. (The acetate filter may be digested with 5 ml of 70 percent nitric acid; this digestion solution may
then be diluted with DI water for total chromium analysis.)

>>>> See the accompanying hardcopy volume for non-machine-readable data that appears at this point.
<<<<

         Note: If the source has a large amount of particulate in the effluent stream, testing teams may
wish to filter the sample twice, once through a 2 to 5-micrometer filter, and then through the
0.45-micrometer filter.

        3.2.5 4.1 Container 2 (HNO3 rinse, optional for total chromium). This sample shall be analyzed in
accordance with the selected procedure for total chromium analysis. At a minimum, the sample should be
subjected to a digestion procedure sufficient to solubilize all chromium present.

         3.2.5.4.2 Container 3 (Silica Gel). Weigh the spent silica gel to the nearest 0.5 g using a balance.
(This step may be conducted in the field.)
                                           +6
       3.2.5.5 Sample analysis. The Cr content of the sample filtrate is determined by ion
chromatography coupled with a post-column reactor (IC/PCR). To increase sensitivity for trace levels of
chromium, a preconcentration system is also used in conjunction with the IC/PCR.

          Prior to preconcentration and/or analysis, all field samples will be filtered through a 0.45- filter.
This filtration should be conducted just prior to sample injection/analysis.

         The preconcentration is accomplished by selectively retaining the analyte on a solid absorbent
(as described in 3.2.3.4.3), followed by removal of the analyte from the absorbent. The sample is injected
into a sample loop of the desired size (repeated loadings or larger size loop for greater sensitivity) and the
   +6
Cr is collected on the resin bed of the column. When the injection valve is switched. the eluent displaces
                    +6
the concentrated Cr sample moving it off the preconcentration column and onto the IC anion separation
                                                              +6
column. After separation from other sample components, Cr forms a specific complex in the
post.column reactor with a diphenylcarbazide reaction solution, and the complex is then detected by
visible absorbance at a wavelength of 520 nm. The amount of absorbance measured is proportional to
                            +6                                                                   +6
the concentration of the Cr complex formed. The IC retention time and absorbance of the Cr complex
                             +6
is compared with known Cr standards analyzed under identical conditions to provide both qualitative
and quantitative analyses.

        Prior to sample analysis, establish a stable baseline with the detector set at the required
attenuation by setting the eluent flowrate at approximately 1 ml/min and post-column reagent flowrate at
approximately 0.5 ml/min.
        Note: As long as the ratio of eluent flowrate to PCR flowrate remains constant, the standard curve
                                                                       +6
should remain linear. Inject a sample of DI water to ensure that no Cr appears in the water blank.

         First, inject the calibration standards prepared, as described in section 3.2.4.4.4, to cover the
appropriate concentration range, starting with the lowest standard first. Next. inject, in duplicate, the
performance audit sample, followed by the 0.1 N KOH field blank and the field samples. Finally, repeat
the injection of the calibration standards to allow for compensation of instrument drift. Measure areas or
                   +6
heights of the Cr /DPC complex chromatogram peak. The response for replicate, consecutive injections
of samples must be within 5 percent of the average response, or the injection should be repeated until the
5 percent criterion can be met. Use the average response (peak areas or heights) from the duplicate
injections of calibration standards to generate a linear calibration curve. From the calibration curve,
determine the concentration of the field samples employing the average response from the duplicate
injections.

        The results for the analysis of the performance audit sample must be within 10 percent of the
reference value for the field sample analysis to be valid.

3.2.6 Calibration. Maintain a written log of all calibration activities.

        3.2.6.1 Sample Train Calibration. Calibrate the sample train components according to the
indicated sections of method 5: Probe Nozzle (section 5.1); Pitot Tube (section 5.2); Metering System
(section 5.3); Temperature Gauges (section 5.5); Leak-Check of the Metering System (section 5.6); and
Barometer (section 5.7).

        3.2.6.2 Calibration Curve for the IC/PCR. Prepare working standards from the stock solution
described in section 3.2.4.4.4 by dilution with a DI water solution to approximate the field sample matrix.
Prepare at least four standards to cover one order of magnitude that bracket the field sample
concentrations. Run the standards with the field samples as described in section 3.2.5.5. For each
standard, determine the peak areas (recommended) or the peak heights, calculate the average response
                                                                              +6
from the duplicate injections, and plot the average response against the Cr concentration in g/L. The
individual responses for each calibration standard determined before and after field sample analysis must
be within 5 percent of the average response for the analysis to be valid. If the 5 percent criteria is
exceeded, excessive drift and/or instrument degradation may have occurred, and must be corrected
before further analyses are performed.

         Employing linear regression, calculate a predicted value for each calibration standard with the
average response for the duplicate injections. Each predicted value must be within 7 percent of the actual
value for the calibration curve to be considered acceptable. If not acceptable, remake and/or rerun the
calibration standards. If the calibration curve is still unacceptable. reduce the range of the curve.

3.2.7 Calculations

       3.2.7.1 Dry Gas Volume. Using the data from the test, calculate Vm(std), the dry gas sample
volume at standard conditions as outlined in Section 6.3 of Method 5.

          3.2.7.2 Volume of Water Vapor and Moisture Content. Using the data from the test, calculate
Vw(std) and Bws, the volume of water vapor and the moisture content of the stack gas, respectively, using
Equations 5-2 and 5-3 of Method 5.

        3.2.7.3 Stack Gas Velocity. Using the data from the test and Equation 2-9 of Method 2, calculate
the average stack gas velocity.
                              +6
        3.2.7.4 Total g Cr        per Sample. Calculate as described below:

m=      (S-B) X V1s X d
where:
                    +6
m=       Mass of Cr in the sample, g.
                                              +6
S=       Concentration of sample, g Cr /ml.
                                           +6
B=       Concentration of blank, g Cr /ml.
V1s =    Volume of sample after filtration, ml.
d=       Dilution factor (1 if not diluted).

>>>> End of File FR94A. This article is continued in File FR94B. <<<<

								
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